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.     

Local canted spin behaviour in Co1.4−x Zn x Ge0.4Fe1.2O4 spinels: A macroscopic, mesoscopic and microscopic study

DC magnetization, neutron depolarization and neutron diffraction (with both polarized and unpolarized neutrons) measurements have been reported for the Co_1.1−x Zn _x Ge_0.1Fe_1.2O₁ spinels with x=0.5, 0.6 and 0.7. Neutron depolarization and neutron diffraction measurements confirm the presence of a long range ferrimagnetic ordering of the local canted spins in these ferrite samples. The observed features of low field magnetization have been explained under the framework of thermally activated domain wall movement of ferrimagnetic arrangement of local canted spins. An important role of magnetic anisotropy (due to the presence of Co²⁺ ions) in establishing the magnetic ordering and domain kinetics in these ferrites has been observed.     

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.     

Transport and Magnetic Properties of Eu and Sr Doped Manganite Compound La0.7Ca0.3MnO3

The effect of simultaneous increase in carrier density and size-disorder on the transport and magnetic properties of La_0.7Ca_0.3MnO₃ has been investigated by studying the (La_{0.7 − 2x} Eu _x )(Ca_0.3Sr _x )MnO₃ (0.05 ≤ x ≤ 0.2) (LECSMO) compounds. These compounds have been compared with standard La_{1 − x} Ca _x MnO₃ (0.3 ≤ x ≤ 0.5) (LCMO) in which carrier density alone varies. In LECSMO, the insulator-metal transition temperature (T _p) decreases from 180 K for x = 0.05 to 80 K for x = 0.15 sample vis-à-vis ∼240 K for x = 0.35 to ∼225 K for x = 0.45 in LCMO system. Similarly, the Curie temperature (T _C) in LECSMO, decreases from 205 K for x = 0.05 to 75 K for x = 0.2 sample against 240 K for x = 0.35 to ∼220 K for x = 0.45 in LCMO system. Also, in LCMO the T _C and T _p are coincident whereas, in LECSMO system, with increasing x there is an increasing disparity between the two. At 5 K, in the metallic region, a large MR (>90%) is observed in x = 0.15 sample and is discussed in terms of phase segregation and inter-grain magnetoresistance.     

Structural and magnetic characterisation of the perovskite oxides La0.7Ca0.3−x Na x MnO3

X-ray powder diffraction (XRD) and magnetic measurements were performed in order to investigate the effect of Na⁺ ion substitution for Ca²⁺ ions on the crystallographic structure, the character of magnetic ordering, and the effect of transition temperature in La_0.7Ca_0.3−x Na _x MnO₃ manganites series (0 ⩽ × ⩽ 0.2). All samples crystallise in an orthorhombic structure with the Pnma space group. We have found a strong dependence of structural and magnetic properties on the cation-size disorder parameter σ ². The temperature dependence of magnetization of all samples obeys the Bloch T ^3/2 law. The values of the spin wave constant at low temperature B increase with the increase of x and the Curie temperature decreases. It is concluded that the substitution of Ca by Na⁺ ions causes a decrease in total exchange integral Aof the samples.      

Conductivity jumps and low-temperature magnetoresistance in the new semiconducting perovskites La1− x BixMnO3+δ

Abrupt jumps are observed on the temperature dependences of the electrical conductivity of La_{1− x} Bi_xMnO_3+δ (0.1<x<0.7) and La_0.3Bi_0.7Na_0.1MnO_3+δ ceramics. The temperatures at which the jumps take place can be reduced by several degrees by applying an external magnetic field of 15 kOe. It can be seen from the magnetization data that the poorly conducting low-temperature phase is not antiferromagnetic (it is likely ferromagnetic) and hence the real-space charge ordering mechanism is not sufficient for explaining the experimental results. An interpretation in terms of magnetic phase nonuniformity is proposed. All the samples studied exhibit high low-temperature magnetoresistance. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 4, 250–253 (25 August 1996) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Effect of high pressure on the crystal and magnetic structures of La<Subscript>0.5</Subscript>Ca<Subscript>0.5</Subscript>CoO<Subscript>3</Subscript> cobaltite

The atomic and magnetic structures of La_0.5Ca_0.5CoO₃ cobaltite have been studied by the neutron diffraction technique at high pressures of up to 4 GPa in the 10- to 300-K temperature range. The pressure dependences of the structural parameters have been obtained. The Curie temperature increases with the pressure with the coefficient dT _C/dP = 1 K/GPa, demonstrating the stability of the ground ferromagnetic (FM) state. The pressure dependence of the ground FM state in La_0.5Ca_0.5CoO₃ is in drastic contrast with that for La_{1 − x} Ca _x CoO₃ at a lower calcium content (x < 0.3). For the latter compound, the pressure suppressed the ground FM state and a large negative pressure coefficient of the Curie temperature (dT _C/dP ∼ −10 K/GPa) was observed. The nature of such a phenomenon is analyzed in the framework of the double exchange model also taking into account the changes in the electron configuration of Co³⁺ ions.     

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.     

Ti/Pr0.7Ca0.3MnO3/La0.67Sr0.33MnO3/Pt异质结电致电阻效应的改善

采用脉冲激光沉积技术制备了Ti/Pr_0.7Ca_0.3MnO₃/Pt和Ti/Pr_0.7Ca_0.3MnO₃/La_0.67Sr_0.33MnO₃/Pt异质结并研究了La_0.67Sr_0.33MnO₃功能插层对异质结电致电阻特性的影响. 实验结果表明La_0.67Sr_0.33MnO₃功能层的引入有效提高了器件的电阻转变特性,尤其是电阻转变率和疲劳性得到了极大的改善. 对La_0.67Sr_0.33MnO₃插层改善电致电阻转变特性的机理进行了定性的分析. 关键词： 电致电阻效应 电阻转变比率 疲劳特性     

Effect of oxygen deficiency on the electrical and magnetic properties of the manganites La1 ? x Ca x MnO3 ? α ( x = 0.5, 0.6, and 0.7)

The electrical conductivity of La_{1 − x} Ca _x MnO_{3 − α} (x = 0.5) alloys in a magnetic field of 0.6 T is investigated in the temperature range 78–300 K. According to the phase diagram, this compound at α = 0 corresponds to an intermediate region between the ferromagnetic conducting (x < 0.5) and antiferromagnetic semiconducting (x s> 0.5) phases and contains islands of the metallic phase. Under oxygen-deficient conditions, the fraction of the metallic phase increases and the semiconductor-metal transition takes place. The formation of bound islands of the metallic phase is observed under oxygen-deficient conditions in the La_0.4Ca_0.6MnO_{3 − α} compounds. Original Russian Text ? Yu.M. Baĭkov, E.I. Nikulin, Yu.P. Stepanov, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 8, pp. 1448–1451.     

Imperfection of the nanostructure, phase transitions, 55Mn NMR, and magnetoresistive properties of La 0.73+ Ca 0.3 ? x2+ Sr x2+ MnO3 ± δ ceramics

Magnetoresistive ceramic samples La_0.7Ca_{0.3 − x} Sr _x MnO_{3 ± δ} sintered at temperatures of 1150 and 1350°C are investigated using X-ray diffraction, microscopic, resistance, and magnetic (χ, ⁵⁵Mn NMR) measurements. The specific features of the influence of the composition on the type and parameters of the perovskite structure, its imperfection, the porous crystallite structure, the metal-semiconductor and ferromagnetic-paramagnetic phase transitions, the ⁵⁵Mn NMR spectra, and the magnetoresistance effect are established. The magnetic phase diagram is constructed. The conclusions are drawn regarding the nonuniformity of the distribution of ions and vacancies around manganese involved in the high-frequency electron-hole exchange (Mn³⁺ ai Mn⁴⁺) and the nanostructured separation of the perovskite structure containing anion and cation vacancies, with the concentrations and magnetoresistance effect decreasing and the lattice parameters and phase transition temperatures increasing as calcium is replaced by strontium. Original Russian Text ? A.V. Pashchenko, A.A. Shemyakov, V.P. Pashchenko, V.A. Turchenko, V.K. Prokopenko, Yu.F. Revenko, Yu.V. Medvedev, B.M. éfros, G.G. Levchenko, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 6, pp. 1127–1136.     

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.     

Electrical transport in La1−x Ca x MnO3 thin films at low temperatures

We report here the low-temperature resistivity of the chemical solution deposited La_1−x Ca _x MnO₃ (x=0.2, 0.3 and 0.33) thin films on LaAlO₃ substrates. The films were post-annealed in atmosphere at 850°C. The low temperature resistivity data has been studied in order to understand the nature of low-temperature conduction processes. The data showed T ² dependence from 60 K to 120 K consistent with the single magnon scattering process. The deviation from this quadratic temperature dependence at low temperatures is attributed to the collapse of the minority spin band. The two-magnon and electron-phonon processes contribute to scattering of carriers in the temperature range above 120 K.     

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.     

Magnetoresistance and electrical conductivity of manganite bicrystal contacts

Magnetic bicrystal contacts in epitaxial films of manganite La_0.67Ca_0.33MnO₃ prepared on bicrystal substrates with a misorientation of the NdGaO₃(110) basal planes rotated through an angle of ±14° around the bicrystal boundary line were studied. The temperature dependence of the contact electrical resistance was studied, and the magnetoresistance was measured in fields of up to 1.5 kOe. It is shown that the suppression of ferromagnetic correlations near the boundary leads to the formation of a layer having a substantially lower Curie temperature. Magnetoresistance of 150%, which is record-braking for bicrystal contacts, was measured at T = 4.2 K in a weak magnetic field of about 500 Oe and at a characteristic electrical resistance of the boundary of 3 × 10⁻⁶ Ω cm². It is found that slight orthorhombic distortions of a La_0.67Ca_0.33MnO₃ film due to a lattice mismatch with the NdGaO₃(110) substrate crystal structure lead to the formation of biaxial magnetic anisotropy in the La_0.67Ca_0.33MnO₃ film.     

Improvement of refrigerant capacity of La0.7Ca0.3MnO3 material with a few percent Co doping

The influence of first and second order magnetic phase transitions on the magnetocaloric effect (MCE) and refrigerant capacity or relative cooling power (RCP) of La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃ materials has been investigated. Large low-field-induced magnetic entropy changes are observed in La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃ materials. The La_0.7Ca_0.3MnO₃ material experiences a large entropy change with a first-order magnetic phase transition at the Curie temperature, T_C. On the other hand, La_0.7Ca_0.3Mn_0.95Co_0.05O₃ displays a smaller entropy change with a second order phase transition. While a first-order magnetic transition material induces a larger MCE (7.528 J/kg K at 5 T) at T_C, this is limited to a narrow temperature range, resulting in a relatively small RCP (218 J/kg), while the Co-doped second-order magnetic transition material induces a smaller MCE (7.14 J/kg K for 5 T), but it is spread over a broader temperature range, resulting in a larger RCP (308 J/kg). The maximum magnetoresistance (MR, defined as ρ(0)/ρ(H)-1) under a field of 5 T is about 206% and 333% for La_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3Mn_0.95Co_0.05O₃, respectively. The refrigeration capacity (RCP) is enhanced in La_0.7Ca_0.3Mn_0.95Co_0.05O₃ (by about 41%) due to small changes from Co doping. The magnetocaloric features of these materials at lower magnetic fields (MCE=3.163 for La_0.7Ca_0.3Mn_0.95Co_0.05O₃ and 4.63 J/kg K for La_0.7Ca_0.3MnO₃ at 1 T), and the high RCP and MR can provide some ideas for exploring novel magnetic refrigerants that can operate with permanent magnets rather than superconducting ones as the magnetic field source.     

Structure and magnetic order in La0.7Ca0.3Mn0.5Co0.5O3 and La0.8Sr0.2Mn0.5Co0.5O3 perovskites

In this paper we report the study of the perovskites La_0.7Ca_0.3Mn_0.5Co_0.5O₃ and La_0.8Sr_0.2Mn_0.5Co_0.5O₃ by neutron powder diffraction at various temperatures and magnetization measurements in zero applied field and at low cooling regimes. The replacement of half Mn by Co in La_0.7Ca_0.3MnO₃ and La_0.8Sr_0.2MnO₃ destroys their long-range ferromagnetism exhibiting a cluster glass ferromagnetic order similar to the one observed in many cobaltites.     

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.     

Thermal and magnetic properties of La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

The thermodynamic and magnetic properties of the La_{1 − x} Pb _x MnO₃ (0.24 ≤ x ≤ 0.40) solid solution system were investigated in the temperature range of 4.2–340 K. All objects were ferromagnetics with Curie temperature T _C ≈ 320–340 K, which slowly increased with x. The M(T) behavior in the magnetic ordering region indicated a nonuniform ground state, due possibly to the competition of ferromagnetic and antiferromagnetic interactions. The increase in the saturation magnetic moment with x can be described by a simple model of the binary bonds in La_{1 − x} Pb _x MnO₃.     

Role of surface phenomena in the magnetoresistivity of polycrystalline manganites La1−x CaxMnO3

The dc electrical resistivity and magnetoresistivity of polycrystalline manganites La_1−x Ca_xMnO₃ (x=0–0.3) are investigated as functions of the temperature, magnetic field and electric field, along with the microwave surface resistance. The investigations show that the dc electrical resistivity and magnetoresistivity are governed by the surface properties of the intergranular boundaries. The dc electrical resistivity is observed to decrease substantially (tenfold) for a comparatively small electric field (E⋟100 V/cm). Estimates are obtained for the internal electrical resistivity of the granules, the thickness of the contact layer (which depends on the temperature and the magnetic field), and the height of the potential barrier between the interfaces separating the surface layer and inner layer of a granule. Fiz. Tverd. Tela (St. Petersburg) 40, 1881–1884 (October 1998)