Electronic excitations in hole-doped La1−xSrxMnO3 studied by resonant inelastic X-ray scattering

We report a resonant inelastic X-ray scattering (RIXS) study on perovskite manganese oxides La_1−xSr_xMnO₃ (x=0, 0.2, and 0.4) at Mn K-absorption edge. Hole-doping effect on the electronic excitations in the strongly correlated electron systems is elucidated by comparing with undoped LaMnO₃. The scattering spectra of metallic La_0.6Sr_0.4MnO₃ show that a salient peak appears in low energies indicating the persistence of the Mott gap. At the same time, the energy gap is partly filled by doping holes and the spectral weight shifts toward lower energies. Though the peak position of the excitations shows weak dispersion in momentum dependence, RIXS intensity changes as a function of the scattering angle (2θ), which is related to the anisotropy. Furthermore, anisotropic temperature dependence is observed in La_0.8Sr_0.2MnO₃ which shows a metal-insulator transition associated with a ferromagnetic transition. We consider that the anisotropy in the RIXS spectra is possibly attributed to the correlation of the orbital degrees of freedom. The anisotropy is large in LaMnO₃ with long-range orbital order, while it is small but finite in hole-doped La_1−xSr_xMnO₃ which indicates persistence of short-range orbital correlation.     

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.     

Magnetic ordering and magnetoresistive effect in La1−x Srx(Mn1−y Mey)O3 perovskites (Me = Nb, Mg)

Perovskites of composition La_1?x Sr_x(Mn_1?x/2Nb _x/2)O₃ and La_0.49Sr_0.51(Mn_1?y Nb_y)O₃ have been synthesized and investigated. The substitution of nonmagnetic niobium ions for manganese was shown to lead to a transition from the metallic into the insulating state due to a decrease in the number of dissimilar (different-valence) manganese atoms in the lattice. In spite of the high resistivity, the niobium-containing perovskites exhibit a large magnetoresistive effect and ferromagnetic ordering. Small additions of Nb⁵⁺ to La_0.49Sr_0.51MnO₃ stimulate the transition from the antiferromagnetic into the ferromagnetic state, whereas the substitution of Mg²⁺ for Mn stabilizes the antiferromagnetic state. It is supposed that the ferromagnetism in the insulating perovskites at hand is due to the positive superexchange of the Mn³⁺-O-Mn³⁺ type, and the magnetoresistive effect owes to the intergranular transfer of spin-polarized charge carriers and the suppression of magnetic nonuniformities by an applied magnetic field near T _C.     

An electron paramagnetic resonance study of phase segregation in Nd0.5Sr0.5MnO3

We present results of an electron paramagnetic resonance (EPR) study of Nd_1−xSr_xMnO₃ with x=0.5 across the paramagnetic to ferromagnetic, insulator to metal transition at 260 K (T_c) and the antiferromagnetic, charge ordering transition (T_N=T_co) at 150 K. The results are compared with those on Nd_0.45Sr_0.55MnO₃ which undergoes a transition to a homogeneous A-type antiferromagnetic phase at T_N=230 K and on La_0.77Ca_0.23MnO₃ which undergoes a transition to coexisting ferromagnetic metallic and ferromagnetic insulating phases. For x=0.5, the EPR signals below T_c consist of two Lorentzian components attributable to the coexistence of two phases. From the analysis of the temperature dependence of the resonant fields and intensities, we conclude that in the mixed phase ferromagnetic and A-type antiferromagnetic (AFM) phases coexist. The x=0.55 compound shows a single Lorentzian throughout the temperature range. The signal persists for a few degrees below T_N. The behaviour of the A-type AFM phase is contrasted with that of the two ferromagnetic phases present in La_0.77Ca_0.23MnO₃. The comparison of behaviour of A-type AFM signal observed in both Nd_0.5Sr_0.5MnO₃ and Nd_0.45Sr_0.55MnO₃ with the two FM phases of La_0.77Ca_0.23MnO₃, vis-à-vis the shift of resonances with respect to the paramagnetic phases and the behaviour of EPR intensity as a function of temperature conclusively prove that the Nd_0.5Sr_0.5MnO₃ undergoes phase separation into A-type AFM and FM phases.     

Manganites at low temperatures and light doping: band approach and percolation

A tight-band model is employed for thee _2g orbitals in manganites. It is shown that a large intra-atomic Hund couplingJ _H and the resulting double-exchange mechanism lead to antiferromagnetic ordering along one of the cubic axes, stabilized by the cooperative Jahn-Teller effect, which further decreases the band energy, of the electrons. As a result, LaMnO₃ is a band insulator built of 2D ferromagnetic layers. The critical concentration (x _c ?0.16) for the onset of ferromagnetic and metallic behavior at low temperatures in La_1?x Sr _x MnO₃ and the phase transition are treated in a percolation approach.     

Origin of the electron spin resonance signal in the manganites: from polarons to phase separation

In the manganites L_1?xM_xMnO₃ (L = La, Nd, Pr, …; M = Sr, Ba, Ca, …), the doping concentration introduces a mixed valence (Mn³⁺, Mn⁴⁺) which governs the magnetic and electric properties of the compound. Mn³⁺ (S = 2) is scarcely observed in electron spin resonance (ESR). In contrast, Mn⁴⁺ (S = 3/2), is a good ESR probe. However, X-band measurements show an enhanced Mn⁴⁺ susceptibility, which is the signature of some kind of coupling of the Mn⁴⁺ ions with the Mn³⁺ ions, but its exact nature is still controversial. We present multifrequency ESR experiments (9–385 GHz) obtained on different systems (La_1?δMnO₃, La_1?xMnO₃, La_1?xCa_xMnO₃, and Nd_1?xCa_xMnO₃) in the low-concentration range (0 <x< 0.33). In the paramagnetic regime, the Mn³⁺ spectrum cannot be observed because of fast relaxation. The signal arises from polarons, whose size, temperature and magnetic field dependences vary with M andx. The single line observed in the metallic compound evolves towards a double-peak structure visible at high frequency in La_0.97MnO₃. Its evolution with temperature below the magnetic transition reveals the presence of manganese ions in a different magnetic environment, i.e., phase separation. The magnetic order of the separated phase is not ferromagnetic. It is a more complex order, which depends substantially on the nature of the cation M.     

铁磁性锰氧化物掺杂的ZnO压敏电阻性能研究

利用通常的电子陶瓷制备工艺制备了铁磁性锰氧化物La_07Sr_03MnO₃掺杂的ZnO陶瓷. 晶界处存在La_07Sr_03MnO₃(LSMO)和LaMnO₃(LMO)两种杂相. 样品中绝缘相LMO的含量显著影响着样品的电学性能. 掺杂后的样品仍具有一定的铁磁性. 在样品上施加磁场后,样品电阻值增加,表现为正磁电阻性质. 正磁电阻的出现,是由于磁场的存在 关键词： ZnO 压敏电阻 锰氧化物 正磁电阻     

Experimental evidence for a magnetic two-phase state in manganites

It is found that samples of manganites La_0.9Sr_0.1MnO₃ (single crystal), Eu_0.7A_0.3MnO₃ (A=Ca, Sr; ceramics), and La_0.1Pr_0.6Ca_0.3MnO₃ and La_0.84Sr_0.16MnO₃ (thin epitaxial films) that are either field-cooled (in a magnetic field) or zero-field-cooled differ in low-temperature magnetization, and the hysteresis loop of field-cooled samples exhibits a displacement. This displacement signifies that a ferro-antiferromagnetic state occurs in these samples. The exchange integral J～10^?6 eV is calculated from this displacement, which describes the exchange Mn-O-Mn coupling through the interface ferromagnetic droplet-antiferromagnetic matrix. The magnetoresistance and volume magnetostriction of La_1?x Sr_xMnO₃ single crystals exhibit similar dependences on x, temperature, and the magnetic field in the vicinity of the Curie point, which points to the fact that these dependences are due to the same reason, namely, the occurrence of a magnetic two-phase ferro-antiferromagnetic state caused by strong s-d exchange.     

Phase transitions induced by a strong magnetic field in electron-doped manganites

The magnetic and magnetoelastic properties of single crystals of electron-doped rare-earth manganites La_1?x Sr _x MnO₃ are studied. Phase transitions from the A-type antiferromagnetic phase to the C-type anti-ferromagnetic phase in a strong magnetic field are revealed in La_1?x Sr _x MnO₃ manganites with a strontium content x = 0.65. A similar phase transition is observed in manganites with a strontium content x = 0.8, at which the La_0.2Sr_0.8MnO₃ manganite is assumed to transform from the C-type antiferromagnetic phase to the G-type antiferromagnetic phase.     

Magnetic ordering in La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3−<Emphasis Type="Italic">x</Emphasis>/2</Subscript> anion-deficient manganites

The structural, magnetic, and electrotransport properties of La_1?xSr_xMnO_{3? x/2}(0≤x≤0.30) manganites with perovskite structure are investigated experimentally as a function of oxygen deficiency. In the solid solutions La_1?xSr_xMnO₃, a change in the type of symmetry of the unit cell is observed at x=0.125. Samples with x≤0.125 are characterized by an O′-orthorhombic unit cell, whereas samples with x>0.125 are characterized by a rhombohedral unit cell. The structural properties of the anion-deficient solid solutions La_1?xSr_xMnO_3?x/2 are analogous to those of the stoichiometric system. It is assumed that, as the oxygen content decreases, La_{1? x}Sr_xMnO_3?x/2 anion-deficient solid solutions experience a series of successive magnetic phase transformations in the ground state: from an A-type (x=0) antiferromagnet to a cluster spin-glass-type inhomogeneous magnetic state (0.175>x≤0.30) through a two-phase (antiferromagnetic and ferromagnetic) state (0>x≤0.175). The anion-deficient solid solution with x=0.175 has the maximal value of the ferromagnetic component. As the oxygen deficiency increases, the resistivity of La_{1? x}Sr_xMnO_3?x/2 samples first decreases (up to a value of x=0.175), acquiring an activation character, and then increases (up to a value of x=0.30). In this case, none of the anion-deficient solid solutions exhibits a metal-semiconductor transition in the whole range of concentrations considered. A peak of magnetoresistance at a temperature below the point of magnetic ordering is observed only in the sample with x=0.175. The results of experiments carried out with a series of La_1?xSr_xMnO_3?x/2 anion-deficient solid solutions are summarized in the concentration diagrams of the spontaneous magnetic moment and the critical temperature of magnetic phase transitions. Hypothetical magnetic phase states are pointed out. The experimental results obtained can be interpreted in terms of the phase-separation model and the competition between ferromagnetic and antiferromagnetic indirect superex-change interactions. It is assumed that Mn³⁺-O-Mn³⁺ indirect superexchange interactions in the orbitally disordered phase are positive in the case of octahedral coordination of manganese ions and are negative when the coordination of at least one Mn³⁺ ion is pentahedral.     

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.     

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.     

Orbital degrees of freedom and electron correlation in optical absorption of metallic LaSrMnO

The optical absorption in ferromagnetic metal La_1-xSr_xMnO₃ is anomalous; it has a wide-range absorption up to about 1 eV even at zero temperature. Since 3d electrons in La_1-xSr_xMnO₃ partially fill doubly degenerate e_g orbitals, the orbital degrees of freedom are crucial to understand this metallic system. We argue that the interband transition within e_g orbitals is important in the optical absorption. The optical spectrum is modified also by the inter-orbital Coulomb interaction. We have examined perturbatively the effect of the Coulomb interaction on the spectrum. Available experiments are discussed by comparing with the present results. Received: 13 February 1998 / Accepted: 17 March 1998     

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.     

Percolative transport in the vicinity of charge-order ferromagnetic transition in a hole-doped manganite

We report measurements of non-linear charge transport in epitaxial (La_1−x Pr _x )_0.7Ca_0.3MnO₃ thin films fabricated on (100) oriented SrTiO₃ single crystals by pulsed laser deposition. The end members of this series, namely Pr_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3MnO₃ are canonical charge-ordered (CO) and ferromagnetic manganites, respectively. The onset of the CO state in Pr_0.7Ca_0.3MnO₃ is manifested by a pronounced insulating behavior below ∼ 200 K. The CO state remains stable even when a large (∼ 2×10⁵ V/cm) electric field is applied across the thin film samples. However, on substitution of Pr with La, a crossover from the highly resistive CO state to a state of metallic character is observed at relatively low electric fields. The current-voltage characteristics of the samples at low temperatures show hysteretic and history dependent effects. The electric field driven charge transport in the system is modelled on the basis of an inhomogeneous medium consisting of ferromagnetic metallic clusters dispersed in a CO background.     

Revival of metastable behavior in phase separated La0.5Ca0.5MnO3+δ

The La_xCa_1−xMnO_3+δ compositions close to charge ordering (x∼0.5) show a gradual relaxation from a metallic/ferromagnetic state to an insulating/antiferromagnetic state with thermal cycling. Here, we report on the magnetic relaxation in the metastable state and also the revival of the metastable state (in a relaxed sample) due to high temperature thermal treatment. We also show the changes in the magnetization and the thermoelectric power as the revived metastable state is cycled. We find that the changes in the thermoelectric power extend well into the region above the charge ordering temperatures. This suggests that the micro-structural changes accompanying the thermal cycling leave their imprint in the paramagnetic insulating state as well.     

Effect of Mo doping on magnetic and transport properties of La0.5Sr0.5CoO3

The substitutional effect of Mo on the magnetic and transport properties of double exchange ferromagnets, La_0.5Sr_0.5Co_1−x Mo_xO₃ (0?x?0.2) has been investigated. Substitution of 10% Mo at the Co-site of La_0.5Sr_0.5CoO₃ decreases the Curie temperature by ∼60 K than that of the parent compound and the long-range ferromagnetic ordering disappears for x?0.2. The Mo-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_c. The insulating state is found to obey Mott's variable range hopping of conduction. The effect of Mo substitution is attributed to the factors namely, (i) the dilution of magnetic Co sublattice, (ii) the reduction of Co⁴⁺/Co³⁺ ratio resulting in a reduced carrier concentration and (iii) disruption of the intermediate spin structure of Co, namely Co³⁺: t_2g⁵e_g¹.     

Conductivity of La1−x CaxMnO3 under magnetic resonance of Mn ions

A change in the electrical conductivity, σ, is observed in the manganese perovskite La_1?x Ca_xMnO₃, with x=0 and 0.3 under saturation of the magnetic resonance transitions of Mn ions. This effect has a maximum in the temperature range of the magnetic phase transition of the compounds. Two contributions to the change in σ are found. The first, dominating in LaMnO₃, is an increase in σ caused by heating of the sample under magnetic resonance. The second is a σ decrease due to reorientation of the Mn spins, observed in La_0.7Ca_0.3MnO₃.     

Itinerant electron theory of transition metal compounds of mixed valency: La1−xSrxMnO3

We use a simplified model to calculate the electronic band structure of compounds of the type of La_1?xSr_xMnO₃. The model includes two nonequivalent sites for the transition metal ions as well as strong Coulomb and exchange interactions between d electrons. Using the resulting band structure we discuss the correlation between magnetic order and conductivity in these compounds.     

Phase separation induced by oxygen isotope substitution in manganites of the Sm<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sr<Subscript>x</Subscript>MnO<Subscript>3</Subscript> system

The effect of ¹⁶O → ¹⁸O isotope substitution on the electrical and magnetic properties of the manganite system Sm_1?xSr_xMnO₃ has been studied. It is shown that oxygen isotope substitution brings about a substantial change in the phase diagram in the intermediate region 0.4<x<0.6 between the ferromagnetic metal and antiferromagnetic insulator regions and induces phase separation and transformation of the ground metallic into insulating state for x=0.475 and 0.5. The specific features of the metal-insulator transitions in the Sm-Sr system and the nature of the low-temperature phase are discussed.