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.     

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.     

Pressure-induced modifications of crystal and magnetic structure of oxygen deficient La<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>MnO<Subscript>3-d</Subscript> manganites

The crystal and magnetic structures of the oxygen deficient manganites La_0.7Sr_0.3MnO_3-d (d = 0.15, 0.20) have been studied by means of powder neutron diffraction over the 0–5.2 GPa pressure and 10–290 K temperature ranges. La_0.7Sr_0.3MnO_2.85 exhibits a coexistence of rhombohedral and tetragonal (I4/mcm) crystal structures and below T_g ~ 50 K a spin glass state is formed. La_0.7Sr_0.3MnO_2.80 exhibits a tetragonal (I4/mcm) crystal structure. Below T_g ~ 50 K a phase separated magnetic state is formed, involving coexistence of C-type AFM domains with spin glass domains. In both compounds the crystal structure and magnetic states remain stable upon compression. The factors leading to the formation of different magnetic states in La_0.7Sr_0.3MnO_3-d (d = 0.15, 0.20) and their specific high pressure behavior, contrasting with that of the stoichiometric A_0.5Ba_0.5MnO₃ (A = Nd, Sm) compounds showing pressure-induced suppression of the spin glass state and the appearance of the FM state, are analysed.     

Structural, magnetic and magnetocaloric properties of La0.7−xEuxBa0.3MnO3 perovskites

Polycrystalline perovskite manganites La_0.7−xEu_xBa_0.3MnO₃(x=0.05, 0.1 and 0.15) were prepared by sol-gel method. The prepared samples remain single phase with a perovskite structure, revealed by X-ray diffraction. The structure refinement of La_0.7−xEu_xBa_0.3MnO₃(x=0.05, 0.1 and 0.15) samples was performed in the hexagonal setting of the R3¯c space group. The dependence of magnetization M on applied magnetic field H and temperature T was measured carefully near the Curie temperature T_C for all the samples. With the increasing Eu content, both the unit cell volume and Curie temperature T_C of 298 K has been detected with a maximum of magnetic entropy |ΔS_M^max| for the La_0.7−xEu_xBa_0.3MnO₃ with x=0.15, reaching a value of 2.3 J/kg K when a magnetic field of 10 kOe was applied and the relative cooling power (RCP) is 46 J/kg. These results suggest that the material may be a suitable candidate as working substance in magnetic refrigeration near room temperature.     

Synthesis and characterization of graphene nanoplatelet-La0.7Ca0.3MnO3 composites

ABSTRACT

La_0.7Ca_0.3MnO₃ perovskite and its composites with graphene nanoplatelet (GNP) were prepared using a wet chemical method. The structural, magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃: GNP composites were investigated to determine the effect of GNPs. The results of XRD analysis show that the synthesised powders can be almost indexed to pure phase orthorhombic La_0.7Ca_0.3MnO_3. The magnetic measurements demonstrate that 0.7 and 1% GNP amounts cause an increase in the Curie temperature (T_C), and for larger amounts of GNP, the T_C monotonically decreases, except for the sample with 10% GNP. The results obtained from the Arrott plots show that the magnetic phase transition of the samples transforms from the first to second order with increasing GNP amount. The changes in the magnetocaloric properties are interpreted in terms of perovskite phase formations via structural analysis. The amounts of graphene nanoplatelets in the oxide powders are correlated with the observed magnetocaloric properties. The best magnetocaloric performance with the maximum magnetic entropy change of 3.99 Jkg^?1K^?1 and refrigeration capacity of 90 Jkg^?1 was obtained at a 2?T magnetic field.     

Magnetoresistance and interlayer exchange coupling in perovskite manganite junctions

We study magnetoresistance (MR) and interlayer exchange coupling (IEC) in perovskite manganite junctions. We show that in La_2/3Sr_1/3MnO₃/SrTiO₃/La_2/3Sr_1/3MnO₃ tunneling junctions, the MR ratio remains finite up to high temperatures near T_C of bulk manganites. In the case of La_2/3Ba_1/3MnO₃/LaNiO₃/La_2/3Ba_1/3MnO₃ metallic trilayers, we predict that the oscillation period of the IEC constant is dramatically changed by hole doping into the LaNiO₃ spacer, while the MR ratio is relatively unaffected.     

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     

Size of the interpolated cation and hole carrier density: two key parameters for the optimisation of colossal magnetoresistive properties of Pr-based manganites

The exploration of the magnetic and transport properties of four series of manganese perovskites, Pr_0.7Ca_0.34−xA_xMnO_3−δ (A=Sr, Ba), Pr_0.7−xLa_xCa_0.3 MnO_3−δ and Pr_0.66Ca_0.34−x Sr_xMnO_3−δ has allowed four phases with colossal magnetoresistive (CMR) properties to be isolated: Pr_0.7Ca_0.25Sr_0.025MnO_3−δ and Pr_0.66Ca_0.26Sr_0.08MnO_3−δ that exhibit a variation of resistance of 2.5. 10⁷% and 10⁹% at μ₀ H=5 T for T=88 K and 50 K respectively, Pr_0.58La_0.12Ca_0.3 MnO_3−δ that exhibits a variation of 6.10⁶% for μ₀ H=5 T at T=80 K and Pr_0.7Ba_0.025Ca_0.275MnO_3−δ for which a resistance variation of 5.10⁹%, at T=50 K, for μ₀ H=5 T is evidenced. for each compound of this series except the barium phase, one observes that the temperature T_max, which corresponds to the resistance maximum on the R(T) curves in zero magnetic field, increases dramatically as the mean size of the interpolated cations increases, and that the CMR effect correlatively decreases dramatically. The comparison of the two series Pr_0.7Ca_0.3−xSr_xMnO_3−δ and Pr_0.66Ca_0.34−xSr_xMnO_3−δ shows also the crucial role of the hole carrier density: for a same mean ionic radius of the interpolated cation T_max is decreased of about 50 K by introducing 0.034 hole per Mn mole.     

Capacitance of the La0.67Sr0.33MnO3/(Ba,Sr)TiO3 interface induced by electric field penetration into the manganite electrode

(001)La_0.67Sr_0.33MnO₃/(001)(Ba_xSr_{1 ? x} TiO₃/(001)La_0.67Sr_0.33MnO₃(x= 0–0.25) three-layer heterostructures are grown by laser evaporation on (001)La_0.3Sr_0.7Al_0.65Ta_0.35O₃ single-crystalline substrates. In a wide temperature range (≈150 K), effective permittivity ? of (1000 nm)Ba_0.25Sr_0.75TiO₃ and (1000 nm)SrTiO₃ films grown obeys the relationship ? ～ (T ? T _CW)^?1, where T _CW is the Curie-Weiss temperature for related bulk crystals. Using experimental dependences ?(T), the capacitance of the (001)La_0.67Sr_0.33MnO₃/(001)Ba_xSr_1?x TiO₃ and (001)La_0.67Sr_0.33MnO₃/(001)SrTiO₃ interfaces, which is due to electric field penetration into the manganite electrode, is estimated (C _int≈4μF/cm²). At bias voltages of ± 2.5 V, the change in the permittivity of the STO and BSTO films in the heterostructures studied reaches 25 and 45%, respectively.     

Response of the electrical resistivity and magnetoresistance of La<Subscript>0.67</Subscript>Ca<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> films to biaxial tensile strains

The structure, electrical resistivity, and magnetoresistance of (50-nm)La_0.67Ca_0.33MnO₃ epitaxial films grown on a [(80 nm)Ba_0.25Sr_0.75TiO₃/La_0.3Sr_0.7Al_0.65Ta_0.35O₃] substrate with a substantial positive lattice misfit have been studied. The tensile biaxial strains are shown to account for the increase in the cell volume and in the relative concentration of Mn⁺³ ions in the manganite films as compared to those for the original material (33%). The peak in the temperature dependence of the resistivity ρ of La_0.67Ca_0.33MnO₃ films was shifted by 30–35 K toward lower temperatures relative to its position in the ρ(T) graph for a manganite film grown on (001)La_0.3Sr_0.7Al_0.65Ta_0.35O₃. For T < 150 K, the temperature dependences of ρ of La_0.67Ca_0.33MnO₃/Ba_0.25Sr_0.75TiO₃/La_0.3Sr_0.7Al_0.65Ta_0.35O₃ films could be well fitted by the relation ρ = ρ₀ + ρ₁T^4.5, where ρ₀ = 0.35 mΩ cm and the coefficient ρ₁ decreases linearly with increasing magnetic field. In the temperature interval 4.2–300 K, the magnetoresistance of manganite films was within the interval 15–95% (μ₀H = 5 T).     

氧非正分La0.9Ba0.1MnO3-δ/SrTiO3:Nb p-n异质结的整流特性研究

利用脉冲激光沉积技术在掺Nb的SrTiO₃衬底上制备了氧非正分La_0.9Ba_0.1MnO_3-δ/SrTiO₃:Nb p-n异质结.在20—300K这一较宽的温度范围内获得了光滑的整流曲线.整流实验表明：该p-n异质结的正向扩散电压V_D随着温度升高在薄膜金属—绝缘转变温度附近出现极大值,表现出与氧正分La_0.9Ba_{0. 关键词： 0.9}Ba_0.1MnO_3-δ薄膜')" href="#">La_0.9Ba_0.1MnO_3-δ薄膜 锰氧化物p-n结 整流性质     

Effects of cation size disorder and lattice distortion on metamagnetism in phase-separated manganites

The effects of A-site cation size disorder in ABO₃ type charge-ordered and antiferromagnetic Pr_0.5Ca_0.5MnO₃ system have been studied by substituting La³⁺, Sr²⁺ or Ba²⁺, while keeping the valency of Mn ions and the tolerance factor (t=0.921) constant in the substituted compounds. We find that the substitutions by these larger cations induce successive sharp step-like metamagnetic transitions at 2.5 K. The critical field for metamagnetism is the lowest for 3% Ba substituted compound, which has the largest A-site cation size disorder and the least distorted MnO₆ octahedra, among the compounds reported here. These cation substitutions give rise to ferromagnetic clusters within antiferromagnetic matrix, indicating phase-separation at low temperatures. The growth of the clusters is found to vary with the substitution amount. The local lattice distortion of MnO₆ octahedra enhances the charge ordering temperature and reduces the magnetization at high fields (>1 T) in these manganites.     

Phase separation in a manganite La<Subscript>0.95</Subscript>Ba<Subscript>0.05</Subscript>MnO<Subscript>3</Subscript> crystal

The structure and magnetic states of a crystal of lightly doped manganite La_0.95Ba_0.05MnO₃ were studied using thermal-neutron diffraction, magnetic measurements, and electrical resistance data in a wide temperature range. It is shown that, in terms of its magnetic properties, the orthorhombic crystal is characterized by two order parameters, namely, antiferromagnetic (T _N = 123.6 K) and ferromagnetic (T _C = 136.7 K). The results obtained differ in detail from known information on the manganites La_0.95Ca_0.05MnO₃ and La_0.94Sr_0.06MnO₃. Two models of the magnetic state of the La_0.95Ba_0.05MnO₃ crystal are discussed, one of which is a model of a canted antiferromagnetic spin system and another is associated with the phase separation of the manganite. Arguments are advanced in favor of the coexistence in this crystal of the antiferromagnetic phase (about 87%) with a Mn⁴⁺ ion concentration of 0.048 and the 1/16-type charge-ordered ferromagnetic phase (about 13%) with a Mn⁴⁺ ion concentration of 0.0625. The specific features of the manganite studied are due to self-organization of the La_0.95Ba_0.05MnO₃ crystal lattice caused by the relatively large barium ion size.     

Size of the interpolated cation and hole carrier density: two key parameters for the optimisation of colossal magnetoresistive properties of Pr-based manganites

The exploration of the magnetic and transport properties of four series of manganese perovskites, Pr_0.7Ca_0.34?xA_xMnO_3?δ (A=Sr, Ba), Pr_0.7?xLa_xCa_0.3 MnO_3?δ and Pr_0.66Ca_0.34?x Sr_xMnO_3?δ has allowed four phases with colossal magnetoresistive (CMR) properties to be isolated: Pr_0.7Ca_0.25Sr_0.025MnO_3?δ and Pr_0.66Ca_0.26Sr_0.08MnO_3?δ that exhibit a variation of resistance of 2.5. 10⁷% and 10⁹% at μ₀ H=5 T for T=88 K and 50 K respectively, Pr_0.58La_0.12Ca_0.3 MnO_3?δ that exhibits a variation of 6.10⁶% for μ₀ H=5 T at T=80 K and Pr_0.7Ba_0.025Ca_0.275MnO_3?δ for which a resistance variation of 5.10⁹%, at T=50 K, for μ₀ H=5 T is evidenced. for each compound of this series except the barium phase, one observes that the temperature T_max, which corresponds to the resistance maximum on the R(T) curves in zero magnetic field, increases dramatically as the mean size of the interpolated cations increases, and that the CMR effect correlatively decreases dramatically. The comparison of the two series Pr_0.7Ca_0.3?xSr_xMnO_3?δ and Pr_0.66Ca_0.34?xSr_xMnO_3?δ shows also the crucial role of the hole carrier density: for a same mean ionic radius of the interpolated cation T_max is decreased of about 50 K by introducing 0.034 hole per Mn mole.     

Mn的价态对La0.8Ba0.2MnO3电磁性能的影响

在2—390K温度之间研究了La_0.8Ba_0.2MnO₃的 磁矩、磁电阻与温度的关系.发 现以不同价态的Mn元素引入得到的La_0.8Ba_0．2MnO₃ ，性能虽然都存在金属 —绝缘体转变，以及在磁场作用下居里温度附近电阻率变化非常显著的特点，但是价态对磁 性转变温度T_C，金属—绝缘体转变温度T_mi，以及磁电阻极大 值温度T_MR的影 响都非常显著.三种价态相比较，使用二价Mn的电阻率最低以及磁性转变温度更接近室温.认 为影响材料性能的主要因素是材料制备时引进的Mn元素的价态，由于原料价态的不同而形成 的氧空位浓度变化，进而影响了Mn⁴⁺/Mn³⁺的比. 关键词： 价态 磁电阻 居里温度 金属—绝缘体转变     

La0.7Ce0.3MnO3 epitaxial films fabricated by a pulsed laser deposition method

La_0.7Ce_0.3MnO₃ epitaxial films were successfully fabricated via a pulsed laser deposition method by controlling the experimental conditions. A series of experiments with varying the oxygen pressure and the substrate temperature demonstrated that the use of appropriate conditions is crucial for fabricating the epitaxial thin films. The existence of such suitable conditions was thermodynamically interpreted in terms of the stability of Mn²⁺ ion. Both XRD and EPMA measurements indicated that La_0.7Ce_0.3MnO₃ thin films fabricated herein form single phases, although it was difficult to present the direct experimental evidence to prove that Ce ion can really exist within the perovskite structure. The resultant films with oxygen annealing showed a metal-insulator transition and ferromagnetic property with Curie temperature of 275 K.     

Response of the electrical resistivity of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript>(20 nm)/LaAlO<Subscript>3</Subscript>(001) films to magnetic field and variation in temperature

The structure, electrical resistivity, and magnetotransport parameters of 20-nm-thick epitaxial La_0.67Ba_0.33MnO₃ films grown by laser ablation on LaAlO₃(001) substrates are studied. The unit cell volume V _eff = 58.80 ų of the as-grown manganite films is found to be less than that for bulk La_0.67Ba_0.33MnO₃ crystals. Maximum values of the negative magnetoresistance MR(μ₀ H = 1 T) = ?0.27 for La_0.67Ba_0.33MnO₃ films are observed at a temperature of about 225 K. For 5 < T < 100 K, the film magnetoresistance depends only weakly on temperature and is on the order of ?0.1. At temperatures below 100 K and for 3 < μ₀ H < 5 T, the electrical resistivity of the as-grown films decreases linearly with increasing magnetic field.     

Relation between giant volume magnetostriction,colossal magnetoresistance,and crystal lattice softening in manganites La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>A<Subscript>y</Subscript>MnO<Subscript>3</Subscript> (A = Ca,Ag, Ba,Sr)

Giant volume magnetostriction (GVM) is detected near the Curie temperature T _C in La_1?x A_xMnO₃ single crystals (A = Ca, Sr, Ba, 0.1 ≤ x ≤ 0.3) and above T _C in La_1?x Ag_yMnO₃ (x = y = 0.15, 0.2 and x = 0.2, y = 0.1) ceramics (in the latter system, giant volume magnetostriction attains a value of 6.5 × 10^?4 in a magnetic field of 8.2 kOe). The behavior of GVM and colossal magnetoresistance (CMR) is found to be the same: both quantities have negative values, the temperature dependences of their absolute values pass through a peak, and the isotherms do not exhibit saturation up to the maximal measuring fields of 130 kOe. In compounds with compositions La_0.7Ba_0.3MnO₃ and La_0.85Ag_0.15MnO₃, GVM and CMR were observed at room temperatures (in a magnetic field of 8.2 kOe, GVM attains values of 2.54 × 10^?4 and 2 × 10^?4 and CMR is equal to 11.6 and 11.2%, respectively). Both phenomena are attributed to the presence of a magnetic (ferromagnetic-antiferromagnetic) two-phase state in these systems, which is associated with a strong s-d exchange. It is found that the maximum value of the GVM in single crystals of La_1?x A_xMnO₃ (A = Ba, Sr, Ca, Ag) depends on the radius R _A of cation A (it is the higher, the larger the difference \(|R_A - R_{LA^{3 + } } |\)). The only exception is the compound with A = Ag, in which the pattern is complicated by additional defectiveness. Local disorder in the La_1?x A_x sublattice, which is associated with the presence of cations with different radii, leads to a displacement of oxygen ions and to crystal lattice softening. The exchange s-d interactions in La_1?x A_xMnO₃ (A = Ca, Sr, Ba, Ag) are found to be comparable with electrostatic interactions ensuring the existence of the crystal; this facilitates manifestation of the GVM.     

Inelastic magnetic X-ray scattering from highly correlated electron systems: La1.2Sr1.8Mn2O7, La0.7Sr0.3MnO3 and Fe3O4

Magnetic Compton profiles have been measured for the colossal magnetoresistance manganites La_1.2Sr_1.8Mn₂O₇ and La_0.7Sr_0.3MnO₃, and for magnetite Fe₃O₄, along various crystallographic directions, over a wide range of temperatures and magnetic fields. The experimental results are interpreted via first-principles computations for the double layer manganite, La_1.2Sr_1.8Mn₂O₇, and by using a simple model involving atomic d-orbitals and free electrons for the other two compounds. For all three materials a preference for the occupation of e_g orbitals is found, particularly, for orbitals of dx²−y² symmetry. An itinerant electron contribution is adduced at all temperatures in magnetite; such a contribution also appears in La_1.2Sr_1.8Mn₂O₇, but it is present only at low temperatures in La_0.7Sr_0.3MnO₃.     

Electron- and Hole-Doping Effects in Manganites Studied by X-Ray Absorption Spectroscopy

We investigate the electronic structures of hole-doped, La_0.7Ca_0.3MnO₃, and electron-doped, La_0.7Ce_0.3MnO₃, manganites by x-ray absorption near edge structure (XANES) spectroscopy at the O and Mn K-edges. While, the O K-edge XANES results indicate that Ca and Ce doping induce holes in O 2p derived states, the Mn K-edge XANES do not give any evidence for creation of the Mn⁴⁺ (or Mn²⁺) ions by Ca (or Ce) dopants. Such results further questions the validity of double exchange mechanism in understanding the anomalous properties of manganites.