Submillimeter and infrared spectroscopy on La0.85Sr0.15MnO3

The optical conductivity of La_0.85Sr_0.15MnO₃ single crystals was studied by means of submillimeter and infrared spectroscopy for frequencies cm^-1 and temperatures 10 K < T <300 K. The submillimeter conductivity follows the temperature dependence of the dc-data. The phonon spectrum of La_0.85Sr_0.15MnO₃ changes considerably below K revealing a structural phase transition induced by charge or orbital order. At T =10 K a number of phonon modes can be identified in addition to the room-temperature spectrum. The optical conductivity () in the mid-infrared reveals the characteristics of small polaron absorption. Below the magnetic ordering temperature the polaron binding energy is highly reduced, but the onset of charge order interrupts the formation of free charge carriers with a Drude-like behavior. The frequency and temperature dependence of in this regime qualitatively resembles the small polaron predictions by Millis et al. (Phys. Rev. B 54, 5405 (1996)). Received 5 November 1999     

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.     

X-ray studies of the (La,Sr)MnO<Subscript>3</Subscript> perovskite manganite structure

X-ray studies of perovskite manganites (La_0.9Sr_0.1)_0.9MnO₃ and La_1?xSr_xMnO₃ (x = 0.1, 0.15, 0.2, 0.25) are reported. The atom positions and interatomic distances and angles are calculated as a function of Sr doping at room temperature using the FullProf software. The temperature dependences of the crystal lattice parameters and unit cell volume are investigated. The effects of structural and magnetic phase transitions on the crystal lattice parameters are studied in detail. The bulk magnetoelastic contribution to thermal expansion is studied experimentally and calculated.     

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.     

Cation disorder and size effects on the magnetic transition in Ba-containing ferromagnetic manganites

The results of ⁵⁵Mn NMR, dc magnetization, and ac susceptibility studies are presented for La_0.7Ca_0.15Ba_0.15MnO₃, La_0.7Sr_0.15Ba_0.15MnO₃, and La_0.7Ba_0.3MnO₃ ferromagnetic manganites. While is a function of the mean radius of the La and alkaline-earth ions and the cation disorder, the form of the temperature dependence of the magnetic moment may be expressed as function of only. The phase transition is continuous for all three compounds. Received 5 March 1999     

Concentration-dependent structural transition in the La0.70Sr0.30MnO3−δ system

The crystal structure of anion-deficient La_0.70Sr_0.30MnO_3?δ manganites (δ = 0, 0.10, 0.15, and 0.20) has been studied by powder neutron diffraction at room temperature. The crystal structures of the stoichiometric La_0.70Sr_0.30MnO₃ and anion-deficient La_0.70Sr_0.30MnO_2.90 samples are satisfactorily described by the rhombohedral R $\bar 3$ c space group. The anion-deficient La_0.70Sr_0.30MnO_2.85 sample separates into two perovskite phases with the R $\bar 3$ c and I4/mcm space groups. The crystal structure of La_0.70Sr_0.30MnO_2.80 cannot be described by a single perovskite phase in the I4/mcm space group. It is found that the clustering of oxygen vacancies is the cause of structural phase separation at 293 K in anion-deficient La_0.70Sr_0.30MnO_3?δ manganites.     

Ferromagnetic superstructure of an La0.85Sr0.15MnO3 manganite single crystal

The elastic thermal-neutron scattering patterns of a La_0.85Sr_0.15MnO₃ manganite orthorhombic single crystal are investigated in the temperature range 4.2–300 K. It is found that, in addition to the known ferromagnetic ordering (T _C=240 K), this compound exhibits a ferromagnetic superstructure with the (010)2π/b wave vector (in the Pnma setting of the space group D _2h ¹⁶ ). The ferromagnetic superstructure is observed in the studied crystal at temperatures ranging from 4.2 to 200 K. It is shown that the formation of the ferromagnetic superstructure in this compound is directly associated with a 1/8-type charge ordering of Mn³⁺ and Mn⁴⁺ ions.     

The relation between magnetoresistance and magnetocaloric effect in La0.85Ag0.15MnO3 manganite

We present the temperature dependence of La_0.85Ag_0.15MnO₃ resistivity in the temperature interval between 77 and 340 K and magnetic fields up to 26 kOe. We offer a method of separating tunnel magnetoresistance from total magnetoresistance. A change in both the magnetic entropy, which is caused by the magnetocaloric effect (MCE), and the magnetoresistance are shown to be connected through a simple relationship to La_0.85Ag_0.15MnO₃.     

Polaron hopping conduction in La0.85Sr0.15MnO3 single crystal

Temperature dependences of electrical resistance and thermopower of a La_0.85Sr_0.15MnO₃ single crystal were measured in the paramagnetic and ferromagnetic dielectric phases. It was shown that charge transfer in both phases is due to the variable-range polaron hopping over the localized states. The activation energies in both phases linearly depend on T ^3/4 but differ from each other by a constant which is approximately equal to the exchange energy kT _c. The results obtained are in compliance with the concept of percolation character of metal-insulator transition in manganites.     

Connection between colossal magnetoresistance in La0.85Sr0.15MnO3 and magnetic ordering inhomogeneities of a sample

Resistive and magnetic measurements are made for La_0.85Sr_0.15MnO₃. The dependence of resistivity on the applied magnetic field (10, 20, 30, and 50 kOe) and temperature (200–310 K) is analyzed using the s-d model and the obtained experimental data. The physical features that should be contained in models proposed to explain the colossal magnetoresistance of manganites with activation-type conductivity are determined. It is shown that the proposed mechanism associating the colossal magnetoresistance effect with phase separation into ferromagnetic and paramagnetic microregions near the Curie temperature has the necessary features.     

Phase separation of the spin system in the La<Subscript>0.93</Subscript>Sr<Subscript>0.07</Subscript>MnO<Subscript>3</Subscript> crystal

The magnetic state of the manganite La_0.93Sr_0.07MnO₃ in the range 4.2–290 K was studied using elastic neutron scattering. The magnetic state of this compound was found to occupy a particular place in the La_1?xSr_xMnO₃ solid-solution system, in which the antiferromagnetic type of order (LaMnO₃, T_N=139.5 K) switches to ferromagnetic ordering (La_0.9Sr_0.1MnO₃, T_C=152 K) with increasing x. In the transition state, this compound contains large-scale spin configurations of two types. A fractional crystal volume of about 10% is occupied by regions of the ferromagnetic phase with an average linear size of 200 Å, while the remainder of the crystal is a phase with a nonuniform canted magnetic structure. Arguments are presented for the phase separation of the La_0.93Sr_0.07MnO₃ spin system being accounted for by Mn⁴⁺ ion ordering.     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

Temperature dependence of the activation energy of manganite conductivity in the paramagnetic phase

The temperature dependence of the magnetic component of the activation energy of hopping conductivity ?_m of manganites in the paramagnetic phase (?_m = ? _m ⁰ ± a/T, where the signs “+” and “?” correspond to the antiferromagnetic CaMnO_{3 ? δ} and ferromagnetic La_0.85Sr_0.15MnO₃ manganites, respectively) has been found and investigated. The results obtained have been qualitatively explained on the basis of the model proposed by Gor’kov and colleagues.     

Oxygen-deficiency and high-pressure effects on the magnetic and crystal structures of La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3−<Emphasis Type="Italic">d</Emphasis></Subscript> managanites

The magnetic and crystal structures of anion-deficient La_0.7Sr_0.3MnO_3?d manganites (d = 0.15 and 0.20) are studied by neutron diffraction in the range of high pressures 0–5 GPa and temperatures 10–300 K. It is found that a spin-glass state forms in La_0.7Sr_0.3MnO_2.85 below T _g ～ 50 K, while magnetic phase separation is observed in La_0.7Sr_0.3MnO_2.80, which is characterized by the coexistence of AFM domains of the C type with spin-glass domains. As distinct from the stoichiometric A_0.5Ba_0.5MnO₃ manganites (A = Nd, Sm), in which the high-pressure effect suppresses the spin-glass state and gives rise to ferromagnetism, the spin-glass state in La_0.7Sr_0.3MnO_2.85 is stable under pressure. The bulk modulus of La_0.7Sr_0.3MnO_2.85 is considerably smaller than that for the stoichiometric La_0.7Sr_0.3MnO₃ compound. The causes of the formation of different types of the magnetic structure in La_0.7Sr_0.3MnO_3?d (d = 0.15 and 0.20) and different high-pressure effects on the magnetic structure of stoichiometric and anion-deficient manganites are analyzed.     

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.     

Metal-insulator transition in a radiation-disordered La<Subscript>0.85</Subscript>Sr<Subscript>0.15</Subscript>MnO<Subscript>3</Subscript> manganite

The temperature dependences of the electrical resistivity ρ(T) and the ac magnetic susceptibility χ(T, H = 0) are thoroughly investigated for a perovskite-like lanthanum manganite, namely, La_0.85Sr_0.15MnO₃, which is preliminarily exposed to neutron irradiation with a fluence _F = 2 × 10¹⁹ cm^?2 and then annealed at different temperatures ranging from 200 to 1000°C. The results of the electrical resistance measurements demonstrate that neutron irradiation of the samples leads to the disappearance of the low-temperature insulating phase. As the annealing temperature increases, the insulating phase is not restored and the manganite undergoes a transformation into a metallic phase. Analysis of the magnetic properties shows that, under irradiation, the ferromagnet-paramagnet phase transition temperature T_C decreases and the magnetic susceptibility is reduced significantly. With an increase in the annealing temperature, the phase transition temperature T_C and magnetic susceptibility χ(_{T, H} = 0) increase and gradually approach values close to those for an unirradiated sample. This striking difference in the behavior of the electrical and magnetic properties of the radiation-disordered La_0.85Sr_0.15MnO₃ manganite is explained qualitatively.     

Thermal expansion of (Sr<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript>x</Subscript>)<Subscript>3</Subscript>Ru<Subscript>2</Subscript>O<Subscript>7</Subscript> single crystals at low temperatures

For single-crystal samples of the (Sr_1?xLa_x)₃Ru₂O₇ ruthenates, the temperature dependence of the thermal expansion coefficient α(T)) is measured in the range 4.2–80 K. The effect of magnetic fields H ≤ 3.5 T on thermal expansion is analyzed. It is found that the (Sr_1?xLa_x)₃Ru₂O₇ ruthenates exhibit an anomalous (negative) thermal expansion coefficient in the temperature range T ≤ 18 K. The position and width of the anomaly revealed in the temperature dependence of the thermal expansion coefficient α(T)) depend substantially on the magnetic field. The origin of the thermal expansion anomaly in ruthenates, the correlation of this anomaly with the stability of the crystal lattice, and the common nature of the anomalies in the thermal properties of ruthenates and high-temperature superconductors are discussed.     

Linear expansion, phase separation, and magnetic inhomogeneities in La0.92Ca0.08MnO3

A relation of the thermal expansion with magnetic and magnetotransport properties has been revealed in La_0.92Ca_0.08MnO₃ single crystals in the paramagnetic state. The magnetotransport and lattice properties and the specific features in the neutron scattering characteristics of the La_0.92Ca_0.08MnO₃ single crystals have been explained by the phase separation in the paramagnetic state into magnetic inhomogeneities (clusters) with short-range (～10 Å) and long-range (>10² Å) orders. The performed investigations have demonstrated that the clusters are closely related to the crystal lattice and that the magnetic inhomogeneities in the paramagnetic region are correlated to T ～ 250–300 K ? TC.     

Defects and the structure of a manganite La0.85Sr0.15MnO3 crystal

Defects in a ferromagnetic crystal of manganite La_0.85Sr_0.15MnO₃ were created by irradiation with fast neutrons (E > 0.1 MeV). Fast neutrons produce defect clusters in a crystal lattice. The volume fraction of the clusters in the crystal after irradiation to a dose F = 2 × 10¹⁹ cm^?2 (T _irr = 340 K) was ?40%. The structural and magnetic states of the modified manganite were studied using thermal-neutron diffraction and magnetic measurements. It was revealed that neutron irradiation of a crystal suppresses the cooperative Jahn-Teller effect and the initial charge modes and decreases the temperature of ferromagnetic ordering. Under irradiation with fast neutrons, the crystalline structure of the manganite changes from the orthorhombic O′ to the pseudocubic O* phase. Arguments are advanced in favor of the specific features of the irradiated-manganite structural state being determined by long-wavelength strains induced in the crystal by antisite defects.     

Crystal structure phase separation in anion-deficient La0.70Sr0.30MnO3 − δ manganite system

The crystal structure of anion-deficient La_0.70Sr_0.30MnO_{3 ? δ} manganite powders (δ = 0, 0.10, 0.15, 0.20) has been investigated at room temperature by the neutron diffraction method using a high-resolution Fourier diffractometer. The structure data have been refined by the Rietveld method. The crystal structures of the stoichiometric La_0.70Sr_0.30MnO₃ and anion-deficient La_0.70Sr_0.30MnO_2.90 manganites are satisfactorily described by the rhombohedral space group R $\bar 3$ c. A small amount of the non-perovskite MnO phase (space group Fm $\bar 3$ m) has been found for the anion-deficient La_0.70Sr_0.30MnO_2.90 sample. It has been found that the anion-deficient La_0.70Sr_0.30MnO_2.85 sample consists of two perovskite phases described by space groups R $\bar 3$ c and I4/mcm and the MnO phase (space group Fm $\bar 3$ m). The crystal structure of the anion-deficient La_0.70Sr_0.30MnO_2.80 sample is described by one perovskite phase with space group I4/mcm. The volume fraction of the MnO phase is ?1% for all anion-deficient samples. Oxygen vacancies in the anion-deficient La_0.70Sr_0.30MnO_{3 ? δ} manganite system stimulate the structure phase separation at 293 K.