The SrFe(2)As(2 - x)P(x) (0.0 ≤ x ≤ 1.0) and CaFe(2)As(2 - y)P(y) (0.0 ≤ y ≤ 0.3) materials were prepared by a solid-state reaction method. X-ray diffraction measurements indicate that the single-phase samples can be successfully obtained for SrFe(2)As(2 - x)P(x) (0.0 ≤ x ≤ 0.8) and CaFe(2)As(2 - y)P(y) (0.0 ≤ y ≤ 0.3). Visible contraction of the lattice parameters is determined due to the relatively smaller radius of P ions in comparison with that of As. The spin-density-wave (SDW) instability associated with the tetragonal to orthorhombic phase transition is suppressed noticeably in both systems following the increase in P content. The highest superconducting transitions are observed at about 27 K in SrFe(2)As(1.3)P(0.7) and at about 13 K in CaFe(2)As(1.925)P(0.075), respectively. Structural analysis suggests that lattice contraction could notably affect the superconductivity in these materials.
Polycrystalline samples of Bi(0.5-y)La(y)Sr(0.5)MnO(3) (0.0≤y≤0.4) (BLSMO) have been synthesized to investigate the Bi(3+) lone-pair effect on the long-range charge-ordering (CO) state. Since the ionic size of La(3+) is similar to that of Bi(3+) and the Mn valence state does not change with La doping, we obtained the Bi lone-pair effect on the CO state without disturbance by other effects. The resistivity ρ(T) and thermoelectric power S(T) of BLSMO have been measured. A hysteretic behaviour was observed in both ρ(T) and S(T) for y = 0.1 and 0.2. From the onset of the hysteretic behaviour, we defined a charge-ordering temperature (T(CO)) and compared it to that of Bi(1-x)Sr(x)MnO(3) (BSMO). Finally, we found that the Bi(3+) lone pairs play an important role in the anomalously high T(CO) in BSMO.
Polycrystalline Mo(3)Sb(7-x)Te(x) samples with nominal Te concentrations of x=0.0, 0.3, 1.0, 1.6 and 2.2 have been synthesized by a powder metallurgical route. High temperature thermoelectric properties measurements including thermopower (300-900 K), electrical resistivity (300-800 K) and thermal conductivity (300-1000 K) were carried out. The temperature and compositional variations of the thermopower can be satisfactorily explained by assuming a single parabolic band model with dominant acoustic phonon scattering. However, such a simple model fails to describe the electronic thermal conductivity for low Te concentration. The dimensionless figure of merit, ZT, increases on increasing both the temperature and the Te content to reach a maximum value of 0.3 at 800 K that can be extrapolated to ∼0.6 at 1000 K for Mo(3)Sb(5.4)Te(1.6).
The nuclear and magnetic structures and properties of Sr0.65Pr0.35-xCexMnO3 (0.00 ≤ x ≤ 0.35) were investigated using a combination of synchrotron x-ray and neutron powder diffraction, along with magnetic and x-ray absorption near edge structure measurements. At room temperature, doping with Ce results in a transition from a tetragonal structure in I4/mcm to an orthorhombic one in Imma associated with the loss of long range orbital ordering. At low temperatures, we observe the formation of an orthorhombic Fmmm phase. XANES measurements demonstrate that the Ce exists as a mixture of Ce(3+) and Ce(4+).
The present paper reports detailed structural and magnetic characterization of the low-bandwidth manganite Pr(1-x)Ca(x)MnO(3) (with x = 0.0-0.5) (PCMO) polycrystalline samples. With increasing Ca content, reduction of the unit cell volume and improvement in perovskite structure symmetry was observed at room temperature. Magnetic characterization shows the signature of coexisting AFM-FM ordering and spin-glass phase at the low doping range (x = 0.0-0.2) while increased hole doping (x = 0.3-0.5) leads to charge ordering, training effect and an irreversible metamagnetic phenomenon. The large irreversible metamagnetism in the CO phase of PCMO and the corresponding spin memory effect is a direct consequence of hysteretic first-order phase transition arising from the weakening of the CO state under the external magnetic field and trapping of the spins due to a strong pinning potential in the material.
The in-plane longitudinal and Hall resistivities, ρxx and ρxy, of superconducting NaFe1-xCoxAs (NFCA) single crystals with x = 0.022 and 0.0205 in the mixed state and the normal state were measured to study the electrical transport properties in nearly optimum-doping iron-based superconductors. The resistivities under magnetic fields show thermally activated behavior and a power law magnetic field dependence of activation energy has been obtained. Due to the weak flux pinning, there is no sign reversal of Hall resistivities observed for NFCA with either x = 0.022 or 0.0205. The correlation between longitudinal and Hall resistivities shows that the scaling behavior of |ρxy| ∝ (ρxx)(β) with the exponent β ≈ 2.0 is in agreement with theoretical predictions for weak-pinning superconductors. Anisotropic upper critical fields and coherence lengths with an anisotropy ratio of γ ≈ 1.63 have been deduced. Furthermore, the normal-state transport properties show that the anomalies of the linear-T resistivity, the T(2)-dependent cotangent of the Hall angle, the linear-T-like Hall number, and the magnetoresistance, which can be scaled by the modified Kohler rule, are analogous to those observed on optimally doped high-Tc superconducting cuprates and other pnictides. The longitudinal resistivity can be understood within a widely accepted scenario of the spin density-wave quantum critical point, while the transverse resistivity requires some further explanation. It is suggested that all the transport anomalies should be simultaneously taken into account when developing theory.
High pressure x-ray diffraction and Raman spectroscopy studies have been carried out on non-stoichiometric sodium tungsten bronze, Na(0.025)WO(3). The high pressure investigations reveal a phase transition at about 2 GPa by a change of space group symmetry from P2(1)/n to P2(1)/c in the monoclinic cell followed by a second structural transformation to a triclinic lattice around 18 GPa. There are volume changes with these structural transformations, which are driven by rotation and significant distortion of WO(6) octahedra due to the displacement of tungsten and oxygen atoms from their mean positions in the unit cell.
We report a structural transition from the orthorhombic to the rhombohedral phase upon size reduction in nanocrystalline LaMnO3+δ (δ ≈ 0.03) as revealed through neutron diffraction studies. The transition occurs when the average particle (crystallite) size is taken below ∼50 nm without change of δ, which is fixed at around 0.03 as measured by a number of characterization tools. The change in the crystallographic structure is accompanied by a change in the magnetic order, where the canted antiferromagnetic order with moments in the basal (ab) plane for the bulk changes to collinear ferromagnetic order with spins along the c-axis for the nanocrystals. The spontaneous ferromagnetic moment ∼3 μB and the transition temperature of 260 K in LaMnO3+δ nanocrystals are similar to those found in La0.67Ca0.33MnO3 which has a much higher Mn(4+) content. The likely origin is traced to change in magnetic exchange interactions due to change in Mn-O bond lengths which become almost identical in the MnO6 octahedron in the rhombohedral structure in the absence of Jahn-Teller distortion. The study provides an example of structural and magnetic phase transition driven purely by size reduction and with no change in the chemical constituents.
The diluted magnetic semiconductors Hg(1-x)Cr(x)Se (0.03≤x≤0.1) were prepared by the solid state recrystallization method. The structure microanalysis of the Hg(1-x)Cr(x)Se compounds, performed by using a scanning electron spectrometer, has shown that the HgCr(2)Se(4) spinel-like inclusions are present in the host matrix Hg(1-x)Cr(x)Se and their amount increases when the chromium content grows. ESR studies of Hg(1-x)Cr(x)Se samples were carried out in the temperature range 4.2-300 K. ESR spectra of the samples with different chromium contents demonstrate the same g-factors at room temperature and similar fine structure development with the temperature decrease. Numerical studies of g-factors, performed by the modified crystal field approach (MCFA), allowed us to reveal that Cr(2+)/Cr(3+) ions in the tetrahedral environment of the solid solution Hg(1-x)Cr(x)Se cannot lead to the ESR signal. The experimental g-factor is well reproduced by a numerical g-factor for Cr(3+) ions located in the octahedral environment, being specific for the HgCr(2)Se(4) spinel phase. The onset of the ESR fine structure is determined by the trigonal distortions of the (CrSe(6))(9-) octahedral cell. From our study it has been found that the spinel clusters are present in the Hg(1-x)Cr(x)Se solid solution even at low chromium content.
A high-pressure Raman scattering study of wolframite-type Mn(0.97)Fe(0.03)WO(4) is presented up to 10.4 GPa. The phonon wavenumbers vary linearly with pressure. The mode Grüneisen parameters are larger for many bending and lattice modes when compared to the stretching modes due to the larger compressibility of Mn(Fe)O(6) octahedra when compared to WO(6) octahedra. Combining the pressure-dependent Raman data of this work with the temperature-dependent Raman data on this crystal previously reported by us has allowed estimation of the temperature-dependent pure lattice and intrinsic anharmonic contributions to the observed total Raman shifts as a function of temperature. It has been found that the observed unusual hardening of the 884, 698 and 674 cm(-1) stretching modes upon heating from 4 to about 150-200 K followed by the usual softening above 150-200 K is a result of a positive intrinsic anharmonic contribution and a negative pure lattice contribution; i.e., up to about 150-200 K the anharmonic contribution surpasses the lattice contribution and the total Raman shift is slightly positive whereas above 150-200 K the lattice contribution becomes dominant and the Raman bands exhibit the usual softening with increasing temperature.
Structural aspects and electronic properties for the Fe(1 + δ)Se(1 - x)Te(x) system with 0.04 ≤ δ ≤ 0.08 and 0.5 ≤ x ≤ 1, especially with the superconducting composition δ is approximately equal to 0.037 and x is approximately equal to 0.55, are investigated comprehensively with x-ray four-circle diffraction and through measurements of electrical resistivity, thermoelectric power, magnetic susceptibility and nuclear magnetic resonance for (125)Te. The crystal structures with an excess Fe site are refined precisely with obvious constraints. For the superconducting composition, the transport properties are explained in terms of the two-band model, where an electron carrier band gives a linear-in-T resistivity and another hole band leads to nearly temperature-independent behaviour. The magnetic susceptibility and the Knight shift are explained with the idea that the electron correlation is enhanced with increasing x and it is reduced with annealing. The spin-lattice relaxation rates for the normal state that show the apparent Korringa relation may also be understood in this framework. These evidences suggest that the superconductivity may emerge in a regime where the correlation is relatively weak in this system.
The magnetization and anisotropic electrical transport properties have been measured in high quality Cu(0.03)TaS(2) single crystals. A pronounced peak effect has been observed, indicating that high quality and homogeneity are vital to the peak effect. A kink has been observed in the magnetic field, H, dependence of the in-plane resistivity ρ(ab) for H is parallel to c, which corresponds to a transition from activated to diffusive behavior of the vortex liquid phase. In the diffusive regime of the vortex liquid phase, the in-plane resistivity ρ(ab) is proportional to H(0.3), which does not follow the Bardeen-Stephen law for free flux flow. Finally, a simplified vortex phase diagram of Cu(0.03)TaS(2) for H is parallel to c is given.
We report a detailed investigation of the magnetocaloric properties of self-doped polycrystalline LaMnO(3+δ) with δ = 0.04. Due to the self-doping effect, the system exhibits a magnetic transition from a paramagnetic to ferromagnetic-like canted magnetic state (CMS) at ~120 K, which is associated with an appreciably large magnetocaloric effect (MCE). The CMS is an inhomogeneous magnetic phase developing due to a steady growth of antiferromagnetic correlation in its predominant ferromagnetic state below ∼120 K. The stabilization of CMS in this material is concluded from a comprehensive analysis of magnetocaloric data using Landau theory, which is in excellent agreement with our neutron diffraction study. The magnetic entropy change versus temperature curves for different applied fields collapse into a single curve, revealing a universal behavior of MCE. Our studies suggest that investigation of MCE is an effective technique to acquire fundamental understanding about the basic magnetic structure of a system with complex competing interactions.
Results of temperature- and magnetic field-dependent strain measurements across the first-order antiferromagnetic to ferromagnetic phase transition in Fe(0.955)Ni(0.045)Rh are presented. Distinct thermal and magnetic field hystereses are observed in the measured strain across the phase transition. The minor hysteresis loops inside the hysteretic regime across the temperature-driven transition are modeled using the Preisach model of hysteresis. The applicability of the Preisach model to explain the general features of minor hysteresis loops is discussed for a disorder influenced first-order transition. The minor hysteresis loops show the property of retaining the memory of the starting or end point of the temperature cycle followed within the hysteretic region. A larger temperature excursion within the hysteretic region wipes out the memory of a smaller temperature cycle which contains one of the extrema of the larger cycle. The end-point memory and the wiping-out property of the minor hysteresis loops can be described quite well within the Preisach model, irrespective of the temperature history followed to reach a particular starting point. Thermo-magnetic history effects across the magnetic field-induced transition are explained, which will enable the choice of the starting point of an experimental cycle in the field-temperature phase space so as to achieve the desired functionality. Our results highlight the necessity to understand the influence of disorder on a first-order phase transition so as to achieve a repeatable performance of materials whose functionalities are based on such a transition.
A resonant x-ray scattering investigation of the NpAs(1 - x)Se(x) system with single crystals of 5 and 10% Se content is reported. The main features of the magnetic phase diagram previously studied by neutron scattering were confirmed. The coexistence within a single domain of ferro- and antiferro-components in the low-T ferrimagnetic phase was established, as well as the single-k character of the incommensurate phase and of the antiferromagnetic component of the ferrimagnetic phase. A tetragonal lattice distortion was found in the ferro- and ferrimagnetic phases which is not compatible with the proposed model for the ferromagnetic phase. The study of ferromagnetism was carried out using polarization analysis of the diffracted beam to separate the scattering intensities originating from magnetism and charge, which are superimposed in reciprocal space. The magnetic character of the ferromagnetic signal calculated from the measured intensities in the polarization analysis σπ and σσ channels was confirmed by analysis of the corresponding temperature dependence.
The crystal structure and thermal expansion of Sr-doped layered cobaltites Y(Ba(1 - x)Sr(x))Co(2)O(5 + δ) (x = 0, 0.05 and 0.10) were studied by means of in situ neutron thermodiffraction in the temperature range 20 K ≤ T ≤ 570 K. The evolution with temperature of lattice parameters for the phases which crystallize in this system is presented, as well as their dependence on the oxygen non-stoichiometry δ. Each phase's volume has been fitted using available models based on the Grüneisen approximation to the zero-pressure equation of state and using the Ruffa model based on the Morse potential, both using a Debye model for the internal energy. The coefficient of volumetric thermal expansion, Debye temperature and other thermodynamic parameters are presented and compared with other perovskite compounds.
We report a 77Se
nuclear magnetic resonance (NMR) investigation on the charge-density-wave (CDW) superconductor
CuxTiSe2 (x = 0.05 and
0.07). At high magnetic fields where superconductivity is suppressed, the temperature dependence of 77Se and 63Cu spin–lattice relaxation
rates 1/T1 follow a linear
relation. The slope of 77Se 1/T1
increases with the Cu doping. This can be described by a modified Korringa relation which
suggests the significance of electronic correlations and the Se 4p- and Ti 3d-band
contribution to the density of states at the Fermi level in the studied compounds.
The electronic structure of superconducting Fe1.03Te0.94S0.06 has been studied by angle-resolved photoemission spectroscopy (ARPES). Experimental band topography is compared to the calculations using the methods of Korringa-Kohn-Rostoker (KKR) with the coherent potential approximation (CPA) and the linearized augmented plane wave with local orbitals (LAPW+LO) method. The region of the Γ point exhibits two hole pockets and a quasiparticle peak close to the chemical potential (μ) with undetectable dispersion. This flat band with mainly dz(2) orbital character is most likely formed by the top of the outer hole pocket or is evidence of a third hole band. It may cover up to 3% of the Brillouin zone volume and should give rise to a Van Hove singularity. Studies performed for various photon energies indicate that at least one of the hole pockets has a two-dimensional character. The apparently nondispersing peak at μ is clearly visible for 40 eV and higher photon energies, due to an effect of the photoionization cross-section rather than band dimensionality. Orbital characters calculated by LAPW+LO for stoichiometric FeTe do not reveal the flat dz(2) band but are in agreement with the experiment for the other dispersions around Γ in Fe1.03Te0.94S0.06.
The crystal structure, dc and ac magnetic susceptibility, electron spin resonance and magnetoresistive behavior of Nd(x)Bi(0.5-x)Sr(0.5)MnO(3) (x = 0.1, 0.2, 0.3 and 0.4) compounds are studied. The Rietveld analysis of the XRD data shows that the samples crystallize in an orthorhombic perovskite structure, with Pbnm space group for x = 0.1 and 0.2 and Imma space group for x = 0.4 and 0.3. Magnetic studies reveal that substituting Bi with Nd collapses the robust charge ordered AFM state of Bi(0.5)Sr(0.5)MnO(3) to an inhomogeneous magnetic state. As Nd concentration increases there is a gradual appearance of cluster glass behavior. ESR studies reveal that the NBSMO system phase separates into ferromagnetic and antiferromagnetic regions below the transition temperature.
We measure systematically the intrinsic scaling behavior of dynamic hysteresis for Pb(0.9)Ba(0.1)(Zr(0.52)Ti(0.48))O(3) (PBZT) ferroelectric thin films with Pt electrodes on Si substrates, utilizing the Sawyer-Tower technique. For the as-prepared thin films of similar thickness and microstructure, over the low frequency range, the scaling follows the power law [Formula: see text] under low E(0) and the power law [Formula: see text] under high E(0), where ⟨A⟩ is the hysteresis area, and f and E(0) are the frequency and amplitude of the external electric field. In the high- f range, the power law for low E(0) takes the form of [Formula: see text], while that for high E(0) takes the form of [Formula: see text]. It is identified that the dynamic behaviors at low frequency mainly come from the intrinsic domain reversal instead of others like the leakage current, while the depolarization field may influence the frequency exponents at high frequency. We study the temperature scaling of the hysteresis, indicating that the scaling under low E(0) is roughly consistent with the (Φ(2))(2) model. Finally, we argue that experimentally obtained power law scaling for Pb(Zr(0.52)Ti(0.48))O(3) thin films prepared under the given conditions may not be reliable due to the polarization fatigue effect.
High-resolution x-ray diffraction (XRD), Raman spectroscopy and total scattering XRD coupled to atomic pair distribution function (PDF) analysis studies of the atomic-scale structure of archetypal BaZrxTi1-xO3 (x = 0.10, 0.20, 0.40) ceramics are presented over a wide temperature range (100-450 K). For x = 0.1 and 0.2 the results reveal, well above the Curie temperature, the presence of Ti-rich polar clusters which are precursors of a long-range ferroelectric order observed below TC. Polar nanoregions (PNRs) and relaxor behaviour are observed over the whole temperature range for x = 0.4. Irrespective of ceramic composition, the polar clusters are due to locally correlated off-centre displacement of Zr/Ti cations compatible with local rhombohedral symmetry. Formation of Zr-rich clusters is indicated by Raman spectroscopy for all compositions. Considering the isovalent substitution of Ti with Zr in BaZrxTi1-xO3, the mechanism of formation and growth of the PNRs is not due to charge ordering and random fields, but rather to a reduction of the local strain promoted by the large difference in ion size between Zr(4+) and Ti(4+). As a result, non-polar or weakly polar Zr-rich clusters and polar Ti-rich clusters are randomly distributed in a paraelectric lattice and the long-range ferroelectric order is disrupted with increasing Zr concentration.
We report the grain size effect of hole-doped cobaltite, La(0.88)Sr(0.12)CoO(3), where average sizes are varied from ∼35 to ∼240 nm. The bulk compound is a cluster-glass (CG) compound composed of short range ferromagnetic (FM) clusters embedded in the spin-glass (SG) matrix at low temperature. The short range FM clusters are still retained in the nanocrystalline compound with average size ∼35 nm which are associated with the SG component, displaying CG-like spin dynamics at low temperature. The exchange bias (EB) effect manifested by the shifts in the hysteresis loop is observed due to the field cooling where EB effect is weakened systematically with decreasing grain size. The decrease in the fraction of the FM component is found to be correlated with the weakening of the EB effect with decreasing grain size. Interestingly, the signature of the EB phenomenon due to the field-cooled effect is also evidenced in the temperature as well as the time dependence of resistivity. The grain interior phase separation scenario around the FM/SG interface region has been proposed to interpret the experimental results.
Samples of the low-doped manganite La(0.875)Sr(0.125-x)Ca(x)MnO(3) (0≤x≤0.125) have been synthesized and the effect on the structural, magnetic and transport properties of decreasing the tolerance factor by replacing larger Sr(2+) ions with smaller Ca(2+) ions are reported. For samples with x≥0.0625, a concentration (x) dependent structural transition (rhombohedral ([Formula: see text]) to orthorhombic (Pnma)) has been detected at room temperature and the Curie temperature T(C) is found to decrease with increased Ca doping level. For samples with x≤0.0625, a narrow metallic region exists and the corresponding insulator to metal transition temperature T(MI) decreases with increasing Ca content, i.e. decreasing tolerance factor. In the paramagnetic region, x dependent crossover from Mott variable range hopping (Mott-VRH) to Shklovskii-Efros variable range hopping (SE-VRH) occurs as the Ca content increases. The thermoelectric power (TEP) of the samples increases substantially, varying inversely with the tolerance factor. These results are analysed from the consideration of increased bending of the Mn-O-Mn bond with the decrease of the average ionic radius of the A-site element [Formula: see text] and the tolerance factor t, which causes narrowing of the bandwidth, decrease of mobility of e(g) electrons and weakening of the double exchange (DE) interaction associated with the substitution of Ca.
The crystal structure, magnetic anisotropy and magnetoelasticity of epitaxial SrTi(0.87)Fe(0.13)O(3-δ) (STF13) and SrTi(0.65)Fe(0.35)O(3-δ) (STF35) films grown on (001), (011), and (111) oriented SrTiO(3) substrates were investigated. The films grew with compressive in-plane strain and underwent tetragonal, monoclinic, and rhombohedral distortions on the (001), (011), and (111) substrates, respectively. All samples showed room temperature magnetic hysteresis loops with strong out-of-plane anisotropy. The resulting magnetoelastic anisotropy was an order of magnitude greater than the magnetocrystalline and shape anisotropies. Magnetoelastic coefficients of B(1) =- 6.7 × 10(6) and B(2) =- 28 to -26 × 10(6) erg cm(-3) for STF13 and B(1) =- 2.0 × 10(6) and B(2) =- 5.4 to -3.9 × 10(6) erg cm(-3) for STF35 were determined from the magnetic anisotropy and lattice strain, corresponding to magnetostriction constants of λ(100) = 2.09 × 10(-6) and λ(111) = 7.68 × 10(-6) for STF13, and λ(100) = 0.62 × 10(-6) and λ(111) = 1.07 × 10(-6) for STF35.
The Li de-intercalation effects for the trimerized state of the geometrically frustrated triangular lattice LiV O(2) are investigated through measurements of x-ray diffraction, magnetic susceptibility and magic-angle spinning-nuclear magnetic resonance (MAS-NMR). Li(1-x)V O(2) with 0 ≤ x ≤ 0.14 obtained with a soft-chemistry synthesis is a single phase. All of the data are understood by considering that the partial substitution for V(3+) (spin-1) with V(4+) (spin-½) leads to the coexistence of the spin-singlet and spin-½ trimers.
A powder of Li(1.3)Al(0.15)Y(0.15)Ti(1.7)(PO(4))(3) has been synthesized by solid state reaction. The powder was a single phase material and had rhombohedral symmetry (space group [Formula: see text]) with six formula units in the unit cell. Impedance spectra of Li(1.3)Al(0.15)Y(0.15)Ti(1.7)(PO(4))(3) ceramics were recorded in the frequency range from 10(6) to 1.2 × 10(9) Hz and temperature range from 300 to 600 K. Two relaxation type dispersions of electrical quantities in the frequency range were found. The dispersion regions are presumably related to the ionic transport processes in bulk and grain boundaries of the ceramics. The activation energy of the conductivity of the bulk and the activation energy of the characteristic relaxation frequency, at which the dispersion sets in, has the same value of 0.25 eV. The only contribution of the mobility of Li(+) ions defines the temperature dependence of the bulk conductivity in the investigated temperature range. The values of ε(') may be related to the contributions of the polarization of the fast ionic migration, vibrations of the lattice and electronic polarization. Nuclear magnetic resonance (NMR) investigation shows that the T(1) of (7)Li and (6)Li at room temperature are 6 ms and 2 s respectively. This result confirms that the relaxation of the (7)Li nucleus occurs through quadrupolar fluctuations although the relaxation of the (6)Li nucleus occurs via dipolar fluctuations. Furthermore, the T(1) minimum allows us to evidence a motion with a characteristic frequency in the range of the Larmor frequency.
Detailed measurements of the magnetic and transport properties of single crystals of La(1-x)Ca(x)MnO(3) (0.18 ≤ x ≤ 0.27) are summarized, and lead to the following conclusions. While temperature-dependent (magneto-) resistance measurements narrow the compositionally modulated metal-insulator (M-I) transition to lie between 0.19 ≤ x(c) ≤ 0.20 in the series studied, comparisons between the latter magnetic data provide the first unequivocal demonstration that (i) the presence of Griffiths-phase-like (GP) features do not guarantee colossal magnetoresistance (CMR), while confirming (ii) that neither are the appearance of such features a prerequisite for CMR. These data also reveal that (iii) whereas continuous magnetic transitions occur for 0.18 ≤ x ≤ 0.25, the universality class of these transitions belongs to that of a nearest-neighbour 3D Heisenberg model only for x≤0.20, beyond which complications due to GP-like behaviour occur. The implications of the variation (or lack thereof) in critical exponents and particularly critical amplitudes and temperatures across the compositionally mediated M-I transition support the assertion that the dominant mechanism underlying ferromagnetism across the M-I transition changes from ferromagnetic super-exchange (SE) stabilized by orbital ordering in the insulating phase to double-exchange (DE) in the orbitally disordered metallic regime. The variations in the acoustic spin-wave stiffness, D, and the coercive field, H(C), support this conclusion. These SE and DE interaction mechanisms are demonstrated to not only belong to the same universality class but are also characterized by comparable coupling strengths. Nevertheless, their percolation thresholds are manifestly different in this system.
We measured the initial M-H curves for a sample of the newly discovered superconductor NdFeAsO(0.82)Fe(0.18), which had a critical temperature, T(c), of 51 K and was fabricated at the high pressure of 6 GPa. The lower critical field, H(c1), was extracted from the deviation point of the Meissner linearity in the M-H curves, which show linear temperature dependence in the low temperature region down to 5 K. The H(c1)(T) indicates no s-wave superconductivity, but rather an unconventional superconductivity with a nodal gap structure. Furthermore, the linearity of H(c1) at low temperature does not hold at high temperature, but shows other characteristics, indicating that this superconductor might have multi-gap features. Based on the low temperature nodal gap structure, we estimate that the maximum gap magnitude Δ(0) = (1.6 ± 0.2) k(B)T(c).
In situ temperature-dependent micro-Raman scattering and x-ray diffraction have been performed to study atomic vibration, lattice parameter and structural transition of proton-conducting Ba(Zr0.8−xCexY 0.2)O2.9 (BZCY) ceramics (x = 0.0–0.8) synthesized by the glycine–nitrate combustion process. The Raman vibrations have been identified and their frequencies increase with decreasing x as the heavier
Ce4+ ions are replaced by
Zr4+ ions. The main Raman vibrations of
Ba(Ce0.8Y 0.2)O2.9 appear near 305, 332, 352, 440 and 635
cm−1. The X–O (
X=Ce, Zr, Y) stretching modes are sensitive to the variation of
Ce/Zr ratio. A rhombohedral–cubic structural transition was observed for x = 0.5–0.8, in which the transition shifts toward higher temperature as cerium increases, except for
Ba(Ce0.8Y 0.2)O2.9. A minor monoclinic phase possibly coexists in the rhombohedral matrix for x = 0.5–0.8. The lower-cerium BZCYs (x = 0.0–0.4) ceramics do not exhibit any transition in the region of 20–900 °C, indicating a cubic phase at and above room temperature.
The magnetic properties together with the crystal and magnetic structures of the cobaltites La(1-x)Ba(x)CoO(3) (for x = 0.2 and 0.3) are determined by DC magnetization, AC magnetic susceptibility and neutron powder diffraction measurements over a broad spectrum of temperatures. For x = 0.3 a rhombohedral structure with space group [Formula: see text] is maintained at all temperatures below 300 K. On the other hand, for x = 0.2 the refinement of the neutron data below 150 K indicates the coexistence of two structures, [Formula: see text] (rhombohedral) and Pbnm (orthorhombic), respectively, in a ratio of ∼48/52. Both compounds (x = 0.2 and 0.3) show a ferromagnetic long range order. The data fit well with the Co(3+) ions in the intermediate spin state and the Co(4+) ions in a low spin state.
The x-ray absorption spectra of Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ) (BSCF) powders quenched in air from 623 and 1173 K were measured at the oxygen K and transition metal L(II,III) edges. All the samples show a predominantly Fe high spin ground state of 3d(5)L character, while the 3d(6)L Co ions are intermediate spin at 623 K and high spin at 1173 K. Further changes in the metal L(II,III) peaks caused by higher temperature quenching are attributed to changes in symmetry around the cations associated with oxygen loss. The oxygen K spectra show the development of unoccupied states just above the Fermi level for samples quenched from 1173 K. At 1173 K, Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ) shows metallic conductivity, while at 623 K it is a semiconductor; the states developed at high temperature with strong oxygen character are pathways for hole conductivity. Splitting of the transition metal 3d energy levels by the ligand field was observed in the oxygen K spectra, and the range for 10Dq is 1.6-1.8 eV, while the 3d bandwidth is 1.1-1.4 eV in samples quenched from 623 K. On the basis of the soft x-ray absorption results, the classification of Ba(1-x)Sr(x)Co(1-y)Fe(y)O(3-δ) as a material with a negative charge-transfer energy is proposed.
In this work, we have studied in detail the temperature dependence of the electric polarization of Eu(0.8)Y(0.2)MnO(3) aimed at clarifying the controversial issues concerning the ferroelectric nature of the lower temperature magnetic phases and hence its multiferroic character. The existence of a spontaneous polarization in 30 K < T < 22 K, provides clear evidence for the ferroelectric character of the re-entrant non-collinear spiral-antiferromagnetic phase, stable in that temperature range. Contrary to results published in previous works, our experimental data clearly show that the weak-ferromagnetic, canted antiferromagnetic phase stable below 20 K is not intrinsically ferroelectric. The misinterpretation, regarding the polar character of the lower temperature magnetic phases, stems from the existence of an induced polarization occurring below 30 K. The mechanisms associated with polar and magnetic properties, and their correlation with both spin and lattice structures are also discussed.
Electrical resistivity, dc magnetization, ac magnetic susceptibility, and magnetic relaxation studies of polycrystalline Pr(0.2)La(0.8)Fe(11.4)Al(1.6) compound have been carried out. On the basis of the measurements of isofield magnetization and ac magnetic susceptibility, we provide evidence for phase coexistence (the appearance of the ferromagnetic phase in the antiferromagnetic matrix) rather than a spin glass, resulting in a cusp observed at ∼70 K in the zero-field-cooled thermal magnetization curve under low fields. The ferromagnetic clusters or nuclei appear randomly in the antiferromagnetic matrix according to the electrical resistivity results. An excellent magnetic-resistive correspondence is observed under medium fields. Under these fields large relaxation effects are presented in the vicinity of the phase transition temperature. Nonuniform variation of the relaxation rate with temperature gives a clear picture of the nucleation and growth of phases. Distinct metastable behavior is shown during the phase transition, which brings about the step-like behavior in the various magnetization curves.
We study the effect of Ga doping at the Ge site of the metamagnetic compound Gd(5)Ge(4). For 5% Ga doping, the resulting alloy (Gd(5)Ge(3.8)Ga(0.2)) shows antiferromagnetic ordering around 130 K, and a thermally driven first order magneto-structural transition at low temperature leading to the ferromagnetic ground state. The alloy shows a noticeable amount of training effect in resistivity when thermally cycled through this first order phase transition (FOPT). The training effect is present in the case of isothermal field cycling. The FOPT region is found to be metastable and extremely sensitive to the applied magnetic field with a clear signature of a metamagnetic transition in the magnetization and resistivity. The metastability is further supported by the large relaxation observed in the resistivity. The giant magnetoresistance observed in the sample is found to be positive near the FOPT, while below the transition it is negative. The resistivity shows irreversibility due to field cycling, which is related to both a field-induced arrested state and some permanent micro-structural changes in the sample.
The polycrystalline (PC) sample of FeCr2S4 displays orbital ordering around TOO ∼ 9 K, while single crystal sample shows orbital glass. In this paper, with the substitution of Al for Cr, a step by step transition from the orbital ordering to the orbital glass is reported in FeCr2-xAlxS4 (0 ⩽ x ⩽ 0.2). For PC FeCr2S4, the onset of long-range orbital order at TOO is evidenced by the appearance of a step-like transition in the temperature dependence of the magnetization (M(T)), a small kink at about 5.5 T below 9 K in the isotherms' magnetic field dependence of the magnetization (M(H)) curves as well as a λ-type anomaly in specific heat. With increasing Al content, the TOO decreases gradually. For the samples with x ⩾ 0.1, the orbital ordering is replaced by orbital glass, where the specific heat obeys a T(2)-dependence. The calculated residual orbital entropy consistently increases with x, implying the progressive freezing of the orbital moments and the coexistence of orbital ordering and orbital glass in the middle doping level.
Pulsed electron deposited thin films of Ru substituted La(1-x)Pb(x)Mn(0.8)Ru(0.2)O(3) (0.2≤x≤0.4) show an increase in the magneto-resistance ratio by ∼5-15% at the respective metal to insulator transition (T(MIT)) temperature when compared to the parent La(0.6)Pb(0.4)MnO(3) thin film. A systematic decrease in T(MIT) is observed from ∼310 to ∼260 K when the hole (Pb) concentration varies from 40 to 20% with constant 20% Ru substitution at the Mn site. The x-ray rocking curve and high-resolution transmission electron microscopy (HRTEM) images of the thin films suggest that Ru occupies the Mn site and shows epitaxial growth of the films on the LaAlO(3) (LAO) substrate. Transport and magneto-resistive properties show that Ru substitution maintains a considerable hole carrier density (due to Mn(4+):t(2g)(3)e(g)(0)/Ru(5+):t(2g)(3)e(g)(0)) even for La(0.8)Pb(0.2)Mn(0.8)Ru(0.2)O(3) (8282) composition, which influences the double exchange interactions.
We have studied the crystal structures of (Sr(0.8)Ce(0.2))(Mn(1-y)Co(y))O(3) (y = 0 and 0.2) using neutron diffraction. Both (Sr(0.8)Ce(0.2))MnO(3) and (Sr(0.8)Ce(0.2))(Mn(0.8)Co(0.2))O(3) have a tetragonal structure in space group I4/mcm at room temperature, and the octahedral tilt angle around the c-axis is nearly the same. The only significant difference is the shape of the Mn(Co)O(6) octahedron: it is elongated in (Sr(0.8)Ce(0.2))MnO(3) due to the cooperative Jahn-Teller (JT) effect, but essentially regular in (Sr(0.8)Ce(0.2))(Mn(0.8)Co(0.2))O(3) due to the absence of JT-active Mn(3+) ions. With increasing temperature, both compounds undergo a continuous phase transition at around 400 °C to a cubic structure in [Formula: see text], with no indication of a distinct transition in (Sr(0.8)Ce(0.2))MnO(3) from the removal of the static JT distortion. In addition, the temperature dependence of the octahedral tilt angle is very similar in the two samples, implying that the JT distortion has minimal effect on the octahedral tilting and the phase transition to cubic. X-ray absorption near-edge structure (XANES) analysis indicates that the Ce oxidation state is predominantly 4+ in both samples. The electrical conductivity is higher in (Sr(0.8)Ce(0.2))MnO(3) than in (Sr(0.8)Ce(0.2))(Mn(0.8)Co(0.2))O(3) in the temperature range studied (100-900 °C).
Polycrystalline samples of Ba(1-x)Sr(x)Fe(2)As(2) (0≤x≤1) and Ba(1-x)Sr(x)Fe(1.8)Co(0.2)As(2) (0≤x≤1) have been synthesized by a solid state reaction method. Structural analysis by means of x-ray diffraction shows that the lattice parameters and unit cell volume decrease monotonically with the increase of x for Ba(1-x)Sr(x)Fe(2)As(2). The measurements of transport properties demonstrate that the average size of the Ba(Sr)-site cations could evidently influence the spin density wave (SDW) behavior in Ba(1-x)Sr(x)Fe(2)As(2) and superconductivity in Ba(1-x)Sr(x)Fe(1.8)Co(0.2)As(2) as well. The critical temperature for SDW (T(SDW)) increases with the Sr substitution for Ba in Ba(1-x)Sr(x)Fe(2)As(2) and, on the other hand, the superconducting T(c) decreases with the increase of Sr content in Ba(1-x)Sr(x)Fe(1.8)Co(0.2)As(2). The inhomogeneous distributions of Ba/Sr ions and structural distortions in Ba(0.5)Sr(0.5)Fe(2)As(2) have been investigated by transmission-electron microscopy (TEM) observations.
A detailed investigation of the paramagnetic to ferromagnetic transition in (La(1-x)Eu(x))(0.67)Ca(0.33)MnO(3) having small Eu(3+)-content (0 ≤ x ≤ 0.2) has been carried out through resistivity and magnetization measurements. X-ray diffraction patterns of the compounds reveal a single phase (La(1-x)Eu(x))(0.67)Ca(0.33)MnO(3) (0 ≤ x ≤ 0.2) of an orthorhombic crystal structure after annealing the precursor at 800 °C for 2 h in air. With increasing Eu(3+)-content, the second-order transition (at x = 0 and 0.1) changes to first-order at x = 0.2. The experimental results demonstrate thermomagnetic irreversibility of the transition for x = 0.2 composition. This arises between the supercooling and superheating regimes where both the ferromagnetic and paramagnetic phases coexist.
The magnetism of CaRu(1-x)Mn(x)O(3)(0.2≤x≤0.9) was studied by the magnetic Compton scattering experiment. The result of the spin-polarized electron momentum density distributions (magnetic Compton profiles) and the absolute value of spin moment indicate that Mn doping introduces magnetic moments on Ru ions, and the Ru and Mn spin moments were antiferromagnetically coupled. Moreover the spin moment of Ru ions increased proportionally in the x range. These results were explained by a mixed valence model and inhomogeneous magnetic structure, where the inhomogeneous magnetic ground state in CaRu(1-x)Mn(x)O(3) would be formed by a ferrimagnetic network from the Mn(3.5+) and Ru(4.5+) clusters in the paramagnetic matrix CaRuO(3) for x<0.5 and in the antiferromagnetic matrix CaMnO(3) for x>0.5.
Crystal structure analyses of the layered compounds Lan(Ti1−xFex)nO3n+2, with nominal compositions x = 0.2 for n = 5 and x = 0.33 for n = 6, show that the iron is concentrated at the centers of the slabs. The spatial arrangements of the iron ions can be approximated by two-dimensional square lattices with strong magnetic interactions between neighboring sites, albeit with fractional occupancies of the sites of an average of 0.67 magnetic ions in n = 6 and 0.42 magnetic ions in n = 5 compounds. A previously described (Lichtenberg et al 2008 Prog. Solid State Chem.
36 253) crossover of magnetic behavior of n = 6 at room temperature is explained by the formation of two-dimensional, ferromagnetically organized magnetic clusters with an average size of 52 Fe3+ ions. The absence of long-range magnetic order follows from the fractional occupancy of the sites by the magnetic ions. The lower concentration of magnetic ions in n = 5 explains why crossover behavior is not found and clusters do not form in that compound.
We report a comprehensive x-ray scattering study of the low-temperature orthorhombic (LTO)-high-temperature tetragonal (HTT) structural phase transition in 1% iron-doped La(2-x)Sr(x)CuO(4) (x = 0.2). The superlattice (032) peak intensity and the width are investigated in detail for a wide temperature range. We found that the structural phase transition is not sharp and the tilt ordering of the CuO(6) octahedra persists above the transition temperature T(S) (≈77 K). Even at room temperature, the superlattice peak is still observable. The structural phase transition is identified as an order-disorder type phase transition. We found that the tilt ordering in our iron-doped material is always short-ranged, and in the HTT phase the correlation between the tilts along the b axis is better preserved than that along the a axis. Moreover, we identify the role of the Fe as the nucleation centers of the LTO domains in the structural phase transition.
The structures of phase-change In(0.21)Sb(0.79) thin film in the amorphous phase were modeled using the reverse Monte Carlo (RMC) method, making simultaneous use of measured x-ray diffraction and x-ray absorption fine structure data. The experimental data that we used do not contain the crystalline phase, which can be observed in the diffraction pattern. Three kinds of initial configurations--a simple cubic lattice, a rhombohedral A7 structure and a dense randomly packed hard sphere form--were used in attempts to reproduce the measured data. The former configuration is thought to be the most probable structure for the crystalline In(0.21)Sb(0.79) thin film. For the latter configuration we could not reproduce the structure of the amorphous In(0.21)Sb(0.79) thin film under the present RMC conditions. We obtained probable structure models for the amorphous In(0.21)Sb(0.79) thin film. We found that the models obtained possess some traces of crystallinity.
We present data on the anisotropic magnetic properties, heat capacity and transport properties of CeGe2-x (x = 0.24) single crystals. The electronic coefficient of the heat capacity, γ ∼ 110 mJ mol(-1) K(-2), is enhanced; three magnetic transitions, with critical temperatures of ≈7, ≈5 and ≈4 K are observed in thermodynamic and transport measurements. The ground state has a small ferromagnetic component along the c-axis. Small applied field, below 10 kOe, is enough to bring the material to an apparent saturated paramagnetic state (with no further metamagnetic transitions up to 55 kOe) with a reduced, below 1.2μB, saturated moment.
The resistivity, magnetization and ultrasonic properties of charge-ordered polycrystalline (Nd(0.75)Na(0.25))(x)(Nd(0.5)Ca(0.5))(1-x)MnO(3) have been investigated from 50 to 300 K. A considerable velocity softening accompanied by an attenuation peak was observed around the charge-ordering transition temperature (T(CO)) upon cooling. The simultaneous occurrence of the charge ordering (CO) and the ultrasonic anomaly implies strong electron-phonon coupling, which originates from the cooperative Jahn-Teller effect. At very low temperature, another broad attenuation peak was observed, which is attributed to the phase separation (PS) and gives a direct evidence of spin-phonon coupling in the compound. With increasing x, T(CO) shifts to lower temperature, the magnetization of the system is strengthened and the PS is enhanced. The temperature dependence of the longitudinal modulus shows that the Jahn-Teller coupling energy E(JT) decreases with increasing Na content. The analysis suggests that the charge mismatch effect may be the main reason for the suppression of the CO and enhancement of the PS.
The transport and superconducting properties of Ho(0.75)Y(0.25)Ni(2)B(2)C single crystals were investigated to study the competing effects between superconductivity and magnetism. The superconducting transition temperature T(c) is 7.6 K, determined from the resistivity transition; meanwhile, the commensurate antiferromagnetic (AFM) transition occurs at T(N) of 3.9 K, which is lower than that of pure HoNi(2)B(2)C (T(N)≈5 K). Ho(0.75)Y(0.25)Ni(2)B(2)C reentered into the normal state at T(m) (T(N)<T(m)<T(c)) when small magnetic fields were applied along the crystallographic c-axis. In contrast to the case in HoNi(2)B(2)C, the reentrant behaviour for Ho(0.75)Y(0.25)Ni(2)B(2)C only appears when the applied field H is along the c-axis, and the reentrant peak position T(P)(H) shifts to lower temperature with increasing applied field. We suggest that the disorder of magnetic structure induced by Y doping may account for the significant difference in the reentrant behaviour between Ho(0.75)Y(0.25)Ni(2)B(2)C and HoNi(2)B(2)C. Moreover, there does not exist a deep minimum in the upper critical field H(c2)(T) line at T(N) of 3.9 K for either [Formula: see text] or [Formula: see text]. The H-T phase diagram is derived and discussed.
The magnetic, structural and electronic properties of Bi(0.75)Ca(0.25)MnO(3) have been investigated in comparison with those of Bi(0.75)Sr(0.25)MnO(3). Magnetometry, diffraction and muon spin relaxation (μSR) data confirm different structural, magnetic and electronic transitions in the two compounds. The anisotropic changes of cell parameters across the structural transition in Bi(0.75)Ca(0.25)MnO(3) (275 K) differ markedly from the lattice anomalies in Bi(0.75)Sr(0.25)MnO(3) (600 K) and also from those in Bi(0.50)Ca(0.50)MnO(3) (325 K). The ground state of Bi(0.75)Ca(0.25)MnO(3) is characterized by a high degree of spin disorder and frustrated interactions. There is no evidence of a ferromagnetic component in the ground state of Bi(0.75)Ca(0.25)MnO(3). However, the application of a magnetic field (even of a few gauss) produces a continuous progressive polarization of the Mn moments (≈2 μ(B)/Mn at 5 T, ZFC, 5 K). Differences between Ca and Sr perovskites with x = 1/4 are greater than for the x = 1/2 counterparts, and point to distinct ground states and charge/orbital configurations.
Electron spin resonance (ESR) spectra of polycrystalline La(0.75)(Ca(x)Sr(1-x))(0.25)MnO(3) (x = 0, 0.45, 1) were studied within the temperature range 110 K≤T≤470 K. The temperature dependence of the ESR intensity for the samples is described by a thermally activated model in the paramagnetic regime. It is found that the activation energy in the orthorhombic phase is higher than that in the rhombohedral phase for La(0.75)(Ca(0.45)Sr(0.55))(0.25)MnO(3). It is suggested that a higher energy is required to destroy the correlated polarons due to the fact that correlated polarons only exist in the orthorhombic phase. This proposition is confirmed by the analysis of the ESR linewidth data, which can be well fitted by the model of adiabatic hopping motion of small polarons. In addition, it is found that, at a fixed temperature, the linewidth decreases with increasing Sr doping, which reveals that the structural tolerance factor has a significant effect on the linewidth.
A high-temperature neutron diffraction study has been carried out on La(0.75)Sr(0.25)CrO(3) compound in the temperature range 300-1400 K. On doping the parent compound LaCrO(3) with Sr at the La site, the orthorhombic (Pbnm) to rhombohedral ([Formula: see text]) structural transition shifts to lower temperatures. From quantitative Rietveld analysis it is found unequivocally that there is a two-phase coexistence (orthorhombic and rhombohedral phases with ∼89 and 11 weight%, respectively) in the temperature range 300-470 K and a three-phase coexistence (with a new cubic phase with space group Pm3m) in the temperature range 480-1400 K. The weight percentages of the orthorhombic, rhombohedral and cubic phases were found to be ∼49%, 37% and 14%, respectively, in the temperature range 480-1300 K, while over 1350-1400 K, the average weight percentages of orthorhombic, rhombohedral and cubic phases were found to be ∼41%, 41% and 18%, respectively. The coefficients of volume thermal expansion and linear thermal expansion have been determined for all three phases. The importance of the present study has been discussed for practical applications of the studied compound in solid oxide fuel cells.
The manganite Nd(0.25)Sm(0.25)Sr(0.5)MnO(3) (NSSMO) shows a first-order metal to insulator transition on cooling, which is concomitant with a magnetic transition from the ferromagnetic to antiferromagnetic state. In some respect the sample shows a striking similarity with Ni-Mn-Sn based ferromagnetic shape memory alloys (FSMAs) undergoing a first-order magneto-structural transition, and efforts have been made to highlight the similarities and dissimilarities of the studied manganite with one such FSMA of composition Ni(2)Mn(1.36)Sn(0.64). From our transport and magnetic investigations, the region of transition in the NSSMO is found to be highly metastable, with a clear indication of a magnetically arrested state which persists even when the sample is cooled down to the lowest temperature of measurement. Interestingly, the studied manganite shows an inverse magnetocaloric effect similar to the FSMA. However, a striking difference between the two compositions is evident in the low-temperature magneto-transport behavior: while a clear signature of tunneling magnetoresistance is present in NSSMO due to the coexisting metallic and insulating clusters of nanometer dimension, the studied FSMA do not show such behavior due to the absence of any insulating phase in the intermetallic alloy.