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.     

Cation ordering and magnetic properties of neodymium-barium manganites

Nd_0.70Ba_0.30MnO_3+δ manganites with an ordered arrangement of Nd³⁺ and Ba²⁺ cations are fabricated. The initial stoichiometric Ba-disordered Nd_0.70Ba_0.30MnO₃ solid solution is synthesized in air using a traditional ceramic technology, is characterized by an orthorhombic unit cell (space group Imma, Z = 4), and is ferromagnetic with Curie temperature T _C ≈ 151 K. The average crystallite size in the initial sample is 〈D〉 ≈ 2.169 μm. Annealing of the initial sample in a reducing atmosphere at a pressure P[O₂] ≈ 10^?4 Pa and then in air at T = 800°C leads to the formation of a material with a crystallite size 〈D〉 ≈ 440 nm. This material consists of the following two perovskite phases: a Ba-ordered stoichiometric NdBaMn₂O₆ phase with a tetragonal unit cell (P4/mmm, Z = 2) and a Curie temperature of ～301 K and a Ba-disordered hyperstoichiometric Nd_0.90Ba_0.10MnO_3+δ phase with an orthorhombic unit cell (Imma, Z = 4) and T _C ～ 121 K. Significant changes in the magnetic properties are explained in terms of chemical phase separation with allowance for cation ordering.     

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.     

Reactance of the n-Au/p-La0.67Ca0.33MnO3 film contact

The responses of the resistance and reactance of Au/(20 nm)La_0.67Ca_0.33MnO₃ film heterostructures to temperature variation and magnetic field (f = 100 kHz) are investigated. At T = 300 K, the capacitance per unit area of the interface between a gold contact and the Au/(20 nm)La_0.67Ca_0.33MnO₃ epitaxial film is found to be about 1 μF/cm². The maximum value of the negative magnetoreactance (≈60% at μ₀ H = 0.4 T) of the heterostructures is almost twice as high as the extremal value of the active magnetoresistance at T ≈ 235 K. The effective depth of magnetic field penetration into the manganite film on the side of the gold contact deposited on its surface is about 3 nm at room temperature.     

Peculiarities of the magnetic state in the system La<Subscript>0.70</Subscript>Sr<Subscript>0.30</Subscript>MnO<Subscript>3−γ</Subscript> (0 ≤ γ ≤ 0.25)

The results of experimental investigation of the chemical phase composition, crystal structure, and magnetic properties of the manganite La_0.70Sr_0.30MnO_3?γ (0 ≤ γ ≤ 0.25) with perovskite structure depending on the concentration of oxygen vacancies are presented. It is found that the mean grain size of the stoichiometric solid solution of La_0.70Sr_0.30MnO₃ amounts approximately to 10 μm, while the grain size for anion-deficient solid solutions of La_0.70Sr_0.30MnO_3?γ is approximately 5 μm. It is found that samples with 0 ≤ γ ≤ 0.13 have a rhombohedral unit cell (with space group \(R\bar 3c\), Z = 2), while samples with γ ≥ 0.20 have a tetragonal unit cell (space group I4/mcm, Z = 2). It is proved experimentally that the magnetic phase state of the manganite La_0.70Sr_0.30MnO_3?γ changes upon a decrease in the oxygen content. It is shown that anion-deficient solid solutions of La_0.70Sr_0.30MnO_3?γ experience a number of successive magnetic phase transformations in the ground state from a ferromagnet (0 ≤ γ ≤ 0.05) to a charge-disordered antiferromagnet (γ = 0.25) via an inhomogeneous magnetic state similar to a cluster spin glass (0.13 ≤ γ ≤ 0.20). The mean size of ferromagnetic clusters (r ≈ 50 nm) in the spin glass state is estimated. It is shown that oxygen vacancies make a substantial contribution to the formation of magnetic properties of manganites. The generalized magnetic characteristics are presented in the form of concentration dependences of the spontaneous magnetic moment, coercive force, and the critical temperature of the magnetic transition. The most probable mechanism of formation of the magnetic phase state in Sr-substituted anion-deficient manganites is considered. It is assumed that in the absence of orbital ordering, a decrease in the magnetic ion coordination number leads to sign reversal in indirect superexchange interactions Mn³⁺-O-Mn³⁺.     

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).     

Effect of lateral tensile stresses on the low-temperature electrical resistivity and magnetoresistance of La0.67Ca0.33MnO3 nanofilms

The thickness of the buffer layer of strontium titanate introduced between an La_0.67Ca_0.33MnO₃ manganite film and a (001)La_0.29Sr_0.71Al_0.65Ta_0.35O₃ substrate is varied (d ₁ = 7–70 nm) to influence effective misfit m in their lattice parameters. As m increases, electrical resistivity ρ of the film increases sharply and the maximum in the ρ(T) dependence shifts toward low temperatures. At T < 150 K, the temperature dependence of ρ of the manganite film obeys the relationship ρ = ρ₁ + ρ₂ T ^4.5, where parameter ρ₁ is independent of the temperature and magnetic field. Coefficient ρ₂ decreases with increasing magnetic field and increases with the misfit between the lattice parameters of the film and substrate, i.e., when the effective hole concentration in the manganite layer decreases.     

Magnetoresistance of La0.67Ca0.33MnO3 films the coherent growth of which is disturbed by mechanical stress relaxation

Because of a large (m = 1.8%) lattice mismatch between La_0.67Ca_0.33MnO₃ and LaAlO₃, manganite films grown on a lanthanum aluminate substrate experience biaxial mechanical compression stresses. Strong adhesion to the substrate causes a substantial tetragonal distortion (γ ≈ 1.04) of the unit cell in a 20-nm-thick layer of the manganite film coherently grown on (001)LaAlO₃, while in the remaining part (≈75%) of the manganite film, stresses partially relax. The stress relaxation decreases γ and increases the effective volume of the unit cell of the La_0.67Ca_0.33MnO₃ film. The relaxed part of the La_0.67Ca_0.33MnO₃ film consists of crystallites 50–200 nm across azimuthally misoriented by approximately 0.3°. The temperature dependences of the resistivity and negative magnetoresistance of the manganite films exhibit maxima at 240 and 215 K, respectively. At temperatures below 50 K, the dependence of the resistivity on the magnetic induction taken with the induction varying from 0 to 14 T and vice versa becomes hysteresis.     

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.     

Effect of phase stratification into electro- and magnetotransport in heteroepitaxial La2/3Ca1/3MnO3 films

The La_2/3Ca_1/3MnO₃ films 25-nm thick biaxially compressed in the substrate plane, grown quasi-coherently on the (001) surface of the LaAlO₃ single crystal, were studied using laser vaporization. It was found that mechanical stresses acting during nucleation and growth promoted calcium enrichment of the cation sublattice of the manganite layer, which caused a decrease in its unit cell volume. Crystalline grains in manganite films were distinctly oriented along the normal to the substrate plane; the grain size in the substrate plane was within 20–40 nm, and the relative grain misorientation in the substrate plane did not exceed 0.2°. In zero magnetic field, the maximum in the temperature dependence of the resistivity ρ of La_2/3Ca_1/3MnO₃ films was observed at temperatures close to 210 K. At T < 100 K and μ₀ H = 2 T, the magnetoresistance of manganite films was negative, weakly depended on temperature, its value was about–0.45. The magnetic field caused transformation of nonferromagnetic phase inclusions to ferromagnetic ones, which resulted in a decrease in the La_2/3Ca_1/3MnO₃ film resistivity with increasing magnetic field. At low temperatures (T < 100 K), a hysteresis was observed in the dependences of the film resistivity on the magnetic field.     

Electrical resistivity and magnetotransport in La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> films asymmetrically biaxially compressed by an NdGaO<Subscript>3</Subscript>(001) substrate

The La_0.67Ba_0.33MnO₃(40 nm) films are quasi-coherently grown on an NdGaO₃(001) substrate with an orthorhombic unit cell distortion of ～1.4%. The biaxial compressive stresses generated during nucleation and growth lead to a decrease in the unit cell volume of the grown layers. This, in turn, results in a decrease (by ～35 K) in the temperature of the maximum in the dependence of the electrical resistivity ρ of the layers on the temperature. For T < 150 K, the electrical resistivity ρ of the films increases in proportion to ρ₂ T ^4.5 and the coefficient ρ₂ decreases almost linearly with increasing magnetic field H. The negative magnetoresistance (≈?0.17 for μ₀ H = 1 T) reaches a maximum at temperatures close to room temperature. The response of the electrical resistivity ρ of the La_0.67Ba_0.33MnO₃(40 nm) films to the magnetic field depends on the crystallographic direction of the film orientation and the angle between H and I (where I is the electric current through the film).     

Magnetoresistance anisotropy in La0.67Ba0.33MnO3 films laterally compressed by a neodymium gallate substrate

The mismatch in the crystal lattice parameters induces biaxial lateral compression of 35-nm La_0.67Ba_0.33MnO₃ films coherently grown on neodymium gallate substrates. Mechanical stresses emerging during the nucleation and growth of the manganite layer facilitate the depletion of this layer in the alkali-earth element. This results in an increase in the unit cell volume in the grown films and a decrease in temperature T _M at which the resistivity attains the maximal value. The extremal values of the negative magnetoresistance (MR ≈ 17% for μ₀ H = 1 T) of the grown films are observed at temperatures close to room temperature. At T < T _M , the response of the resistivity of the films to the magnetic field depends on the direction of this field relative to the normal to the substrate plane and to the direction of the measuring current. At T = 95 K, scattering of holes from 90°-domain walls leads to an increase in the resistivity of the manganite films by approximately 1.1%, while the negative anisotropic magnetoresistance reaches 1.5%.     

Electrical resistivity and magnetotransport properties of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>MnO<Subscript>3</Subscript> epitaxial films biaxially compressed by the substrate

The structure, electrical resistivity, and magnetoresistance of La_0.67Ba_0.33MnO₃(20 nm) films grown coherently on an La_0.3Sr_0.7Al_0.65Ta_0.35O₃(001) substrate with a lattice misfit of about 1% were studied. The rigid connection of the manganite layer with the bulk substrate brought about the unit cell distortion of the substrate (a _⊥/a _‖ = 1.02) and a decrease in the unit cell volume as compared to that of the corresponding bulk crystals (a _‖ and a _⊥ are the unit cell parameters measured in the substrate plane and along the surface normal, respectively). The temperature T _M ≈ 295 K, at which the electrical resistivity ρ of the (20 nm)La_0.67Ba_0.33MnO₃ films reached a maximum, was 40–45 K lower than that for the corresponding bulk crystals. The negative magnetoresistance (MR ≈ ?0.25 for μ₀ H = 1 T) attained a peak value at T _MR ≈ 270 K. The response of ρ to a magnetic field depended substantially on the angle between the current flow in the film and the direction of the magnetic field.     

Structure and magneto-transport parameters of partially relaxed and coherently grown La0.67Ba0.33MnO3 films

X-ray diffraction (XRD) and medium-energy ion scattering (MEIS) have been used to reveal distortions in the crystal lattice of La_0.67Ba_0.33MnO₃ (LBMO) films formed in relaxation of mechanical stresses. The LBMO films 25 nm thick have been prepared by laser deposition. The XRD and MEIS data obtained suggest that biaxially and mechanically elastically stressed LBMO layers grow coherently on LSATO substrates, whose crystal lattice parameter differs only weakly from the corresponding LBMO parameter, whereas in the bulk of manganite films grown on LaAlO₃ substrates, stresses relax partially. Stresses do not relax in the LBMO interface about 4 nm thick adjoining LaAlO₃. The electro- and magneto-transport parameters of partially relaxed LBMO films have been compared with those obtained for coherently grown manganite films with approximately the same tetragonal distortion of the lattice cell (a _⊥/a _‖ = 1.024–1.030; a _‖ and a _⊥ are the unit cell parameters in the substrate plane and normal to it, respectively). At temperatures substantially lower than the Curie temperature, the electrical resistivity ρ of LBMO films fits the relation ρ = ρ₀ + ρ₁ T ² + ρ₂(H)T ^4.5; the coefficients ρ₀ and ρ₁ do not depend on temperature T and magnetic field, and ρ₂ does not depend on temperature but almost linearly decreases with increasing magnetic field strength H. The coefficient ρ₂ for partially relaxed LBMO films is substantially larger than that for coherently grown manganite layers.     

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.     

Destruction of manganite La0.825Ba0.175MnO3 ferromagnetism caused by structural disordering

The methods of neutron diffraction, X‐ray and magnetic measurements were used to study the structural and magnetic states of disordered samples of manganite La_0.825Ba_0.175MnO₃. A disordered state was attained by irradiation with fast neutrons. It was established that the ferromagnet → spin glass‐like magnetic transformation takes place at a substitution concentration of ～6%. A magnetic state diagram of structurally disordered manganite was constructed. The magnetic state transformations are explained by the effect of localization of e _g‐electrons responsible for kinetic ferromagnetic exchange. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Exchange bias tuned by cooling field in La0.2Ca0.8MnO3 nanoparticles

We report the magnetic properties in the nanosized charge ordering manganite La_0.2Ca_0.8MnO₃ with an average particle size ～50 nm. The sample exhibits ferromagnetism at low temperatures. The exchange bias phenomenon is observed when the sample is cooled down in an external magnetic field. Moreover, the exchange bias field is dependent on the cooling field and shows a maximum of ～520 Oe under a cooling field ～5 kOe. The exchange bias effect can be attributed to the exchange coupling between the ferromagnetic shell and antiferromagnetic core. The decrease of exchange bias field in high cooling field can be attributed to the growth of ferromagnetic component under high cooling field.     

Penetration of electromagnetic field through the La-Er-Ba manganite far above the magnetic phase transition temperature

Using the technique of penetration of electromagnetic waves through the bulk samples of La_0.60Er_0.07Ba_0.33MnO₃ manganite, it is shown that in this class of strongly correlated materials the local dynamic magnetic ordering is preserved at the temperature by 66 K above the Curie temperature where the static long-range magnetic order is absent. In this temperature range the dynamic magnetic permeability exceeds unity and is frequency dependent. The average lifetime of local ordered states is estimated.     

Influence of the granule size on the magnetocaloric properties of manganite La0.5Ca0.5MnO3

The influence of the granule size on the magnetic and magnetocaloric properties of ceramic sample of manganite La_0.5Ca_0.5MnO₃ has been investigated. Anomalies indicating the coexistence of the ferromagnetic metallic and antiferromagnetic charge-ordered phases below T _C have been found in the temperature dependence of the magnetocaloric effect. It has been shown that a decrease in the granule size to 90 nm leads to the complete suppression of the antiferromagnetic charge-ordered phase.     

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.