Crossover of polaron conductivity and the inhomogeneous state of lanthanum manganites in the magnetic phase transition region

The transport properties of lanthanum manganites over a wide range of temperatures below the magnetic phase transition point are discussed within the model of a two-phase composite whose phases differ in the magnetic order and charge carrier concentration. The volume ratio of the phases depends on the temperature and the magnetic field. The magnetoelastic polarons are charge carriers in both phases, and the metal-dielectric transition occurs as a percolation transition accompanied by the crossover of the polaron conductivity. The results obtained by numerical simulation of the resistivity, magnetoresistance, and thermopower are compared with the experimental data for La_0.7Mn_1.3O_3?δ thin films. The theoretical and experimental data are in good agreement.     

Ferromagnetic lanthanum manganites

The short overview of the physical properties of the ferromagnetic manganites exhibiting colossal magnetoresistance is given.     

Elastic properties of lanthanum manganites

We give a brief overview of the data on elastic properties of the CMR manganites published during last decade. The main emphasis is put on the results obtained for single crystals.     

Giant thermal hysteresis in lanthanum manganites

The giant thermal hysteresis of the longitudinal sound velocity and internal friction turns out to be a specific feature of the orthorhombic-to-rhombohedral structural transition in La_1−xSr_xMnO₃ and La_1−xBa_xMnO₃ manganites. The mixture of the orthorhombic and rhombohedral phases can exist far beyond the thermal hysteresis loop as it is observed in magnetization or resistivity experiment. This means that in the CMR manganites, the boundary between the crystal phases is fuzzy.     

Electromagnetic field penetration through lanthanum manganites

The process of electromagnetic field penetration through lead-doped lanthanum manganites exhibiting colossal magnetoresistance has been studied. The measurements have been performed in a range of radio frequencies from 20 kHz to 10 MHz in the temperature interval containing a magnetic phase transition. Application of a constant external magnetic field leads to an increase in the transmission coefficient. Relative variations of the electromagnetic field transmission coefficient are several times as large as the relative change in the dc magnetoresistance. The temperature dependence of the relative change in the transmission coefficient has been studied. Variations of the transmission coefficient sharply decrease in the vicinity of the phase transition temperature, but they still remain rather large at temperatures above the Curie point.     

Optical evidence for lattice polarons in lightly doped lanthanum manganites in paramagnetic state

The reflection and absorption spectra and the resistivity data for La_0.93Sr_0.07MnO₃, La_0.9Sr_0.1MnO₃, La_0.85Sr_0.15MnO₃, La_0.92Ca_0.08MnO₃ and La_0.85Ba_0.15MnO₃ single crystals have been collected and analyzed by using small lattice polaron theory. The activation energies of the polaron hop are determined. The lattice polarons are found to be dominated in the electronic transport and optical properties in the paramagnetic state in La_0.93Sr_0.07MnO₃, La_0.92Ca_0.08MnO₃ and La_0.85Ba_0.15MnO₃ crystals. It is shown that lattice polaron involves more than one Mn site.     

Magnetic inhomogeneity of lanthanum manganites single crystals

The magnetic inhomogeneity of the single crystals of La_1−xD_xMnO₃, where D=Ca, Sr, Ba, is studied. The Curie temperature distribution function is found. The form of this function is shown to depend on whether the mean value of the divalent element concentration is close to the “optimal” concentration (≈1/3) or not. The standard deviation for Curie temperature is evaluated. The correlation between the distribution coefficient for divalent elements and the standard deviation is established.     

Magnetoresistance of lanthanum manganites with activation-type conductivity

The temperature dependence of the resistivity and magnetic moment of La_0.85Ba_0.15MnO₃ and La_0.85Sr_0.15MnO₃ manganite single crystals in magnetic fields up to 90 kOe is investigated. Analysis of the experimental results shows that the magnetoresistance of lanthanum manganites far from the Curie temperature T _C can be described quantitatively by the s-d model normally used for ferromagnets and taking into account only the exchange interaction between the spins of charge carriers and magnetic moments. These data also show that the features of lanthanum manganites responsible for colossal magnetoresistance (CMR) are manifested in a narrow temperature interval δT ≈ 20 K near T _C. Our results suggest a CMR mechanism analogous to the mechanism of giant magnetoresistance (GMR) observed in Fe/Cr-type multilayers with nanometer layer thickness. The nanostratification observed in lanthanum manganites and required for GMR can be described taking into account the spread in T _C in the CMR range δT.     

Competition between structural and electronic factors in (Al/In) doped lanthanum manganites

X-ray structure parameters of La_0.7Ca_0.3Mn_0.96(In_xAl_(1−x))_0.04O₃ perovskite manganites determined from the Rietveld analysis of the orthorhombic unit cell, space group Pbnm, showed strong dependence on x. Resistivity (ρ) and ac magnetic susceptibility (χ) measurements showed decrease in the metallic-to-semiconductor transition temperature T_ρ and the ferromagnetic-to-paramagnetic Curie temperature T_C as x increases. The large drop in T_ρ and T_C for x=0.0 and 1.0 is ascribed to the difference between the electronic configuration (E-factor) and ionic radius (structure factor) of the dopants and the Mn³⁺ ions. Decrease in T_ρ and T_C for samples (0.2<x<0.8) is mainly due to the size mismatch between the A and B sites (structure factor).     

Room-temperature phase separation in weakly doped lanthanum manganites

The properties of single crystals of weakly doped lanthanum manganites La_1?xA_xMnO₃ (A = Ca, Ce, Sr; x = 0, 0.07?0.1) have been studied in the temperature range from 77 to 400 K. It is established that these lanthanum manganites exhibit (in addition to the well-known characteristic features observed in the region of the temperature of magnetic ordering) changes in the electrical and magnetic properties in the region of room temperature (T ≈ 270–300 K), which is about two times the Curie temperature (T ≈ 120–140 K) and is far from the temperature of structural transitions in the samples studied. The results are explained in terms of phase separation related to the formation of magnetic clusters in the nonconducting medium. The phase separation is caused by a gain in the exchange energy and by the development of elastic stresses in the crystal lattice and proceeds via combination of small-radius magnetic polarons into a large-size magnetic cluster containing several charge carriers. The short-range order in the cluster appears and the phase separation begins at a temperature T_ps, which is close to T_C ≈ 300 K, typical of doped conducting manganites. The results of magnetic measurements show that, as the temperature decreases from 300 to 190 K, the size of superparamagnetic droplets increases from about 8 to 15 Å.     

Intrinsic inhomogeneities of low-doped lanthanum manganites in the paramagnetic temperature range

The nature of the electrical resistivity for low-doped lanthanum manganites is elucidated. The electrical resistivity is described by the Efros-Shklovskii law (lnρ √ (T ₀/T)^−1/2, where T ₀ √ 1/R _ls) in the temperature range from T* ≈ 300 K ≈ T _C (T _C is the Curie temperature for conducting manganites) to their T _C and is explained by the tunneling of carriers between localized states. The magnetoresistance is explained by a change in the size of localized states R _ls in a magnetic field. The patterns of change in R _ls with temperature and magnetic field strength determined from magnetotransport properties are satisfactorily described in the model of phase separation into small-radius metallic droplets in a paramagnetic matrix. The sizes R _ls and their temperature dependence have been estimated through magnetic measurements. The results confirm the existence of a Griffith phase. The intrinsic inhomogeneities produced by thermodynamic phase separation determine the electrical resistivity and magnetoresistance of lanthanum manganites.     

Critical behavior studies in Ti-substituted lanthanum bismuth perovskite manganites

Perovskite manganite La_0.4Bi_0.6Mn_1−xTi_xO₃ (x = 0.05 and 0.1) synthesized using conventional solid state route method give rise to critical phenomenon in their magnetic interactions due to the substitution of non magnetic Ti ions. The critical behavior is observed near paramagnetic–ferromagnetic transition and is studied by magnetization measurements. Various techniques like Modified Arrott plot, Kouvel–Fisher method, scaling equation of state analysis and the critical magnetization isotherm were used to analyze the magnetization data on magnetic phase transition. The values of critical exponents β and γ obtained using different techniques are in good agreement. The obtained critical exponents are found to follow scaling equation with the magnetization data scaled into two different curves below and above the transition temperature, T_C. This confirms that the critical exponents and T_C are reasonably accurate. The obtained critical exponents for both the samples deviates from mean-field model and do not completely follow the static long range ferromagnetic ordering. This behavior is consistent with non magnetic nature of Ti substituted at Mn site and can be associated with Griffiths phase like phenomenon.     

Electrochemical promotion of propane deep oxidation on doped lanthanum manganites

Electrochemical catalysts based on LSM deposited on YSZ were used for propane deep oxidation. Electrochemical characterizations such as impedance spectroscopy and current–overpotential measurements were performed. Different thicknesses of LSM films were catalytically characterized and EPOC experiments were carried out on those electrochemical catalysts. It was found that the reaction rates can be in situ tuned by applying an anodic polarization but with weak promotional effects. The faradaic efficiency decreased as the applied potential, the temperature, and the thickness of the catalyst increased. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007.     

Contribution of carriers to optical conductivity spectra of lanthanum manganites

To study the band structure and carriers in lanthanum manganites, measurements have been made of the reflectance spectra of single crystals and polycrystals in the 0.04–1.6-eV range and of the optical conductivity σ _opt calculated by the Kramers-Kronig method as functions of the concentration and species of divalent ions in the paramagnetic (PM) and ferromagnetic (FM) regions. The optical gap for single-crystal La_0.9Sr_0.1MnO₃ is ∼0.17 eV, and the polaronband energy is 0.12 eV. In the PM region, σ _opt spectra do not indicate a band-carrier contribution, and conduction is dominated by polaron hopping and activation to the mobility edge. In the FM region, the variation in the σ _opt and absorption spectra of La_0.7Sr_0.3MnO₃ epitaxial films indicate the appearance of band carriers and a red shift of the absorption edge. The two band-carrier contributions, with weak and strong dependences on photon energy, are related to conduction in the antiferromagnetic matrix and the ferromagnetic regions. Fiz. Tverd. Tela (St. Petersburg) 41, 475–482 (March 1999)     

Centers of charge nonuniformity in absorption spectra of lanthanum manganites

In order to study the microscopic nature of the phase separation in lanthanum manganites, experimental investigations were made of the optical, electrical, and magnetic properties of La_1?δMnO₃ and La_0.9Sr_0.1MnO₃ lanthanum manganite single crystals. The infrared absorption spectra revealed two bands at 0.14 eV and 0.35 eV whose intensity was sensitive to the magnetic order. The different temperature dependence of the electrical resistivity (semiconducting) and the transmission (metallic) below the Curie ferromagnetic temperature indicates that an insulator-metal transition takes place in various regions of the insulating matrix, i.e., phase separation occurs. Characteristic features of the properties and the nature of the phase separation in these compounds can be explained using a model of polar (hole [MnO ₆ ^8? ] _JT and electron [MnO ₆ ^10? ] _JT ) pseudo-Jahn-Teller clusters which form centers of charge nonuniformity in the crystal.     

Magnetic and high-pressure magnetotransport properties of cesium-substituted lanthanum calcium manganites

The nature of the double-exchange (DE) interaction in lanthanum manganites is studied through chemical substitutions, Cs for La, and high-pressure measurements. Static and high-frequency magnetic measurements and high-pressure electrical transport studies were carried out on bulk polycrystalline and radio-frequency sputtered thin films of La_0.7-xCs_xCa_0.3MnO₃ for x=0-0.1. The samples are found to be cubic. Curie temperature T_c measurements provide evidence for bond-length-related weakening of DE as x is increased from 0 to 0.03. For higher x, the bond-angle-related changes lead to an increase in the strength of DE. High-pressure mangetoresistance data indicate both bond length and bond-angle-related increase of 10–20 K/GPa in T_c with pressure, with the largest increase measured for x=0.03. The rate of increase in the Curie temperature with pressure decreases with increasing T_c. Anomalies are observed in the magnetic parameters for x=0.03. The Cs-concentration dependence of the low-temperature saturation magnetization shows a minimum close to x=0.03. Ferromagnetic resonance studies at x-band reveal a 5% decrease in the g-value for x=0.03 relative to the end members (x=0 and 0.1). The low-field magnetostriction for x=0.03 indicates a relatively strong electron–phonon spin coupling compared to neighboring compositions. Received: 15 May 2000 / Accepted: 24 July 2000 / Published online: 9 November 2000     

Thermoelectric power of potassium doped lanthanum manganites at low temperatures

The temperature-dependent resistivity and thermoelectric power of monovalent (K) doped La_1−xK_xMnO₃ polycrystalline pellets (x=0.05, 0.10 and 0.15) between 50 and 300 K are reported. K substitution enhances the conductivity of this system. Curie temperature (T_C) also increases from 260 to 309 K with increasing K content. In the paramagnetic region (T>T_C), the electrical resistivity is well represented by adiabatic polaron hopping, while in the ferromagnetic region (T<T_C), the resistivity data show a nearly perfect fit for all the samples to an expression containing, the residual resistivity, spin-wave and two-magnon scattering and the term associated with small-polaron metallic conduction, which involves a relaxation time due to a soft optical phonon mode. Small polaron hopping mechanism is found to fit well to the thermoelectric power (S) data for T>T_C whereas at low temperatures (T<T_C) in ferromagnetic region (S_FM), S_FM is well explained with the spin-wave fluctuation and electron–magnon scattering. Both, resistivity and thermopower data over the entire temperature range (50–300 K) are also examined in light of a two-phase model based on an effective medium approximation.     

Efros-Shklovskii law and localized states in weakly doped lanthanum manganites

The existence of clusters in weakly doped lanthanum manganites at temperatures about twice as high as their Curie temperature T _C has been shown. Electrical resistance in weakly doped lanthanum manganites obeys the Efros-Shklovskii law. The temperature and magnetic-field dependences of a cluster size determined from the magnetotransport properties have been described using the model of phase separation into small metallic droplets within the dielectric paramagnetic and antiferromagnetic matrices. The results agree with the existence of the Griffiths phase.     

Phase separation and anisotropy in the electrical properties of weakly doped lanthanum manganites

Variations in the thermopower, electrical resistivity, magnetoresistance, thermal expansion coefficients, and their anisotropy with temperature were detected near room temperature in single crystals of weakly doped lanthanum manganites La_1?xA_xMnO₃ (A = Ca, Sr; x = 0.07–0.125) with orthorhombic structure. The results obtained are discussed in terms of a model of phase separation related to polaron anisotropy. Due to a gain in exchange and elastic energies in the lattice, small-radius magnetic polarons can merge to form polarons of a larger size, which would contain now not one but rather a few electrons (equal in number to the polarons in the cluster). As a result, short-range order in a cluster and phase separation set in at a temperature T_ps ≈ 250–300 K, which is approximately equal to the Curie temperature T_C of conducting manganites with x ≈ 0.2–0.3.     

The effects of vacancies in oxygen sites on physical properties of the lanthanum manganites

Abstract

The non-stoichiometric solution Ln_1?xSr_xMnO_3-δ□_δ was prepared by the classic ceramic method. The physical properties as crystallographic, magnetic and electrical properties were studied. A structural phase transition from rhombohedral to orthorhombic was observed at a concentration of Mn⁴⁺ between 10% and 15% per Mn atom in the unit formula. The magnetic properties are very sensitive to the presence of vacancies at the oxygen sites. The non-stoichiometric, samples change from metallic to insulating behaviour depending on their vacancy concentration. In the semiconductor phase, the activation energy value changes with the structural phase, increasing in the rhombohedral phase and decreasing in the orthorhombic phase.