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.     

Structural features of the La-Sr-Fe-Co-O system

A structural study has been performed on the La_0.8Sr_0.2Fe_xCo_1-xO₃ (x = 0.025 to 0.3) system displaying large magnetoresistance (MR) at room temperature. A detailed analysis of the crystal structure and microstructure was done by X-ray diffraction (XRD), transmission and scanning electron microscopy (TEM and SEM). The atomic resolution TEM images and the appearing superreflections in the corresponding SAED patterns revealed that a superstructure is formed due to the presence of iron. The correlation between the ordered microstructure and the observed large MR ratio is discussed. ⁵⁷Fe M?ssbauer spectroscopy was utilized to gain information on the valence state of iron in the sample with x = 0.3. The lattice parameters of Fe- doped La_0.8Sr_0.2Fe_xCo_1-xO₃ compounds were found to increase monotonously with increasing Fe content. The valence state of iron was found to be Fe³⁺. Received 22 January 2001     

Low temperature specific heat of bi-layered manganites La2−2xSr1+2xMn2O7 (x=0.3 and 0.5)

The specific heat (C) of bi-layered manganites La_2−2xSr_1+2xMn₂O₇ (x=0.3 and 0.5) is investigated for the ground state of low temperature excitations. A T^3/2 dependent term in the low temperature specific heat (LTSH) is identified at zero magnetic field and suppressed by magnetic fields for x=0.3 sample, which is consistent with a ferromagnetic metallic ground state. For x=0.5 sample, a T² term is observed and is consistent with a two-dimensional (2D) antiferromagnetic insulator. However, it is almost independent of magnetic field within the range of measured temperature (0.6-10 K) and magnetic field (6 T).     

Structural, magnetic and transport properties in the manganites La0.7Sr0.3−xTexMnO3 (0≤x≤0.15)

The effect of Te-doping at La-site on structural, magnetic and transport properties in the manganites La_0.7Sr_0.3−xTe_xMnO₃ (0≤x≤0.15) has been investigated. All samples show a rhombohedral structure with the space group . It shows that the Mn-O-Mn bond angle decreases and the Mn-O bond length increases with the increase of Te content. The Curie temperature T_C decreases with increasing Te-doping level, in contrast, the magnetization magnitude of Te-doping samples at low temperatures increase with increasing x as x≤0.05 and then decrease with further increasing x to 0.15. The results are discussed in terms of the combined effects of the opening of the new double exchange (DE) channel between Mn²⁺-O-Mn³⁺ due to the introduction of Mn²⁺ ions because of the substitution of Te⁴⁺ for Sr²⁺ and the reduction of the transfer integral b due to the decrease of the Mn-O-Mn bond angle.     

钙钛矿锰氧化物La0.7Sr0.3MxMn1-xO3(M=Cr,Fe)的巨磁电阻效应与磁性

研究了溶胶-凝胶法制备氧化物巨磁电阻材料的工艺,制备了La_0.7Sr_{0.3< /sub>CrxMn1-xO3(x=0,0.10,0.15)和La0.7Sr0.3FexMn1-xO3(x=0.05,0.10,0.16)两 系列的单相钙钛矿锰氧化物多晶样品,并研究了Cr,Fe替代La0.7Sr0.3MnO3中部分Mn后对其结构、磁性和巨磁电阻性质的影响.观察到La0.7 Sr0.3Cr0.15Mn0.85O3和La0. 7Sr0.3Fe0.05Mn0.95O3两个样品的 电阻-温度曲线都出现了双峰.定性讨论了可能产生双峰的机制.随Cr(或Fe)替代量的增加, 材料的居里温度很快下降,铁磁性减弱,导电性降低,巨磁电阻效应增强.但与Fe掺杂相比 ,相同数量的Cr掺杂对材料的影响要小. 关键词： 巨磁电阻效应 溶胶-凝胶工艺 电阻-温度曲线 金属绝缘体转变}     

Synthesis and characterization of La0.7Sr0.3Mn1−x TixO3 manganites

The structural, electrical and magnetic properties of the La_0.7Sr_0.3Mn_1?x Ti_xO₃ system characterized by rhombohedral lattice distortions are studied. Substitution of titanium for manganese weakens ferromagnetism and leads to an increased resistivity. Using x-ray Rietveld full-profile refinement data and ferromagnetic resonance spectra, it is demonstrated that titanium substitution for manganese occurs with charge compensation according to the equation Mn⁴⁺ → Ti⁴⁺ and with a simultaneous decrease in the oxygen nonstoichiometry as the value of x increases.     

Magnetic phase transitions and magnetoresistance in the La0.7Ba0.3(Mn1−xMex)O3 (Me=Fe,Al) single crystals and La0.7Sr0.3(Mn1−xMex)O3 (Me=Fe,Cr, Al) ceramics

The single crystals of La_0.7Ba_0.3(Mn_1−xFe_x)O₃ (x⩽0.28) and La_0.7Ba_0.3(Mn_1−xAl_x)O₃ (x⩽0.15) compositions were grown using flux method and characterized by X-ray, electrical and magnetization measurements. The Fe-doping above x=0.2 destroys a long range ferromagnetic order thus leading to a spin glass state. It is found that insulating spin glasses exhibit a large magnetoresistance in the paramagnetic region which is comparable to that for ferromagnetic crystals showing metal–insulator transition close to T_C. The magnetic behavior of La_0.7Ba_0.3(Mn_1−xMe_x)O₃ (Me=Fe, Cr, Al) ceramics is in agreement with superexchange magnetic interactions via oxygen.     

Structural and magnetic phase diagram and room temperature CMR effect of La1−xAgxMnO3

The study of the structural and magnetic phase diagram of the manganites La_1−xAg_xMnO₃ shows similarity with the La_1−x′Sr_x′MnO₃ series, involving a metallic ferromagnetic domain at relatively high temperature (≈300 K). The Ag-system differs from the Sr-one by a much smaller homogeneity range (x≤1/6) and the absence of charge ordering. But the most important feature of the Ag-manganites deals with the exceptionally high magnetoresistance (−25%) at room temperature under 1.2 T, that appears for the composition x=1/6. The latter is interpreted as the coincidence of the optimal double exchange condition (Mn³⁺:Mn⁴⁺=2) with T_max=300 K (maximum of the ρ(T) curve in zero field).     

Laser patterning and magnetic properties of perovskite-type La0.7Sr0.3MnO3 crystals on the glass surface

The laser-induced crystallization technique has been applied to 10La₂O₃-35SrO-25MnO₂-30B₂O₃ glass (mol%) in order to examine the possibility of the formation and morphology control of perovskite-type La_1?xSr_xMnO₃ crystals on the glass surface. It is found from X-ray diffraction analyses that La_0.7Sr_0.3MnO₃ crystals are formed in the sample obtained by continuous wave Y b:Y V O₄ fiber laser (wavelength: 1080 nm) irradiations (power: 350 mW, scanning speed: 10 μm/s). La_0.7Sr_0.3MnO₃ manganites in the laser-irradiated samples are proposed to be ferromagnetic crystals having a Curie temperature of ～315 K from magnetization measurements and the Arrott plot. The surface morphology of laser-irradiated parts is not smooth, and La_0.7Sr_0.3MnO₃ crystals are present randomly without any orientations. It is clarified that Mn⁴⁺ ions in the glass act as suitable transition metal ions for the laser-induced crystallization.     

Magnetization and resistivity steps in the phase separated PrCaMn NiO manganites

The low temperature magnetic and transport properties of the Pr_0.5Ca_0.5Mn_1-xNi_xO₃ manganites ( 0≤ x ≤0.1) have been investigated. The presence of Ni hinders the charge and orbital ordering observed in Pr_0.5Ca_0.5MnO₃ and favors the creation of ferromagnetic regions, leading to phase separation. The ferromagnetic fractions induced by the Ni substitution have been estimated from magnetization measurements, they are large and reach 40% for 4% of Ni. Steps are observed in the M ( H ) and ρ( H ) curves of all the samples at T < 5 K. They are similar to the steps observed in Pr_0.5Ca_0.5Mn_1-xM_xO₃, where M is a non magnetic cation (Mg²⁺, Ga³⁺,...), and for which the ferromagnetic fractions are very small (less than 2%), however, their appearance is restricted to lower temperatures (T < 5 K) with Ni dopant than with non magnetic cations. This study shows that steps can be observed in a wide range of phase-separated systems, even when the ferromagnetic fraction is very large. Received 5 April 2002 / Received in final form 8 July 2002 Published online 14 October 2002 RID="a" ID="a"e-mail: antoine.maignan@ismra.fr     

Magnetic exchange interactions induced by Cr-doping in perovskite manganites

The effect of Cr-doping on the structural, magnetic and transport properties of perovskite manganites La_0.8Ca_0.2Mn_1−xCr_xO₃ (0≤x≤0.7) has been investigated. The Curie temperature (T_C) of the Cr-doped samples is almost unchanged up to 30% of Cr-doping. The Cr-doped samples, however, undergo a transition from the parent metallic state to the insulating state below T_C. The dc and ac magnetization data suggest that ferromagnetic clusters induced by double exchange interaction between Cr³⁺ and Mn³⁺ ions and antiferromagnetic components driven by Cr³⁺/Mn⁴⁺ and Cr³⁺/Cr³⁺ interactions are present in the Cr-doped system, which is supported by comparative studies on magnetic and transport properties of LaMnO_3+δ and LaMn_0.75Cr_0.25O_3+δ.     

The correlation between structure and magnetic properties in the manganites La0.7Ca0.3−xTexMnO3 (0≤x≤0.15)

The effect of Te-doping at La-site on structural, magnetic and transport properties in the manganites La_0.7Ca_0.3−xTe_xMnO₃ (0≤x≤0.15) has been investigated. All samples show an orthorhombic structure (O′-Pbnm) at room temperature. It shows that the Mn-O-Mn bond angle decreases and the Mn-O bond length increases with the increase in the Te content. All samples exhibit an insulator-metal (I-M) transition and the resistivity increases with the increase in the Te-doping level. Additionally, the Curie temperature T_c decreases and the transition becomes broader with increasing Te-doping level, in contrast, the magnetization of Te-doping samples at low temperatures decrease with increasing x as x≤0.10 and then increase with further increasing x to 0.15. The results are discussed in terms of Jahn-Teller (JT) vibrational anisotropy Q₃/Q₂ and the opening of the new DE channel between Mn²⁺-O-Mn³⁺ due to the introduction of Mn²⁺ ions because of the substitution of Te⁴⁺ ions for Ca²⁺ ions.     

Magnesium,a promising dopant for the improvement of the CMR properties of perovskite manganites

The study of the substitution of magnesium for manganese in the type I Pr_0.7(Ca,Sr) _0.3MnO₃ and type II Pr_0.5Sr_0.5MnO₃ manganites has been performed. Remarkable colossal magneto resistance (CMR) properties have been evidenced for the manganites Pr_0.7Ca_0.2Sr_0.1 Mn_{1 x}Mg_xO₃, with x ≤ 0.02, for which R_OT/R_7T resistance ratio values ranging from 10⁴ to 4.10⁵ at 105 K and 70 K respectively were obtained in a magnetic field of 7 T. The study of the type II phases Pr_0.5Sr_0.5M_{1 x}Mg_xO₃, shows their similarity with the trivalent metal doped manganites Pr_0.5Mn_1?x M_xO₃ with M = Al, Ga, In, in contrast to the tetravalent metal doped manganites with M = Ti, Sn. The latter properties are interpreted in terms of two factors, the molar ratio Mn(III): Mn(IV), and the size of the doping cation.     

Mössbauer studies of new CMR compounds (La1-xSnx)2(Mn0.985Fe0.015)2Oy

Mössbauer spectra of (La_1-xSn_x)₂(Mn_0.985Fe_0.015)₂O_y (x=0.2, 0.3, 0.4 and 0.5) from room temperature to 4.2 K have been studied; in addition X‐ray diffraction patterns at room temperature have been obtained. The results show that the phase compositions of (La_1-xSn_x)₂(Mn_0.985Fe_0.015)₂O_y are strongly dependent on the Sn concentrations and on the heat treatment. The manganites with x=0.2, 0.3 and 0.4 after annealing in air at 1200°C appear to consist of two phases, ABO₃ and A₂B₂O₇. Their Mössbauer spectra are paramagnetic doublets at room temperature that become sextets at T ～ 230 K and ～ 60 K. The ABO₃ phase appears to be the source of the CMR in manganite (La_0.7Sn_0.3)₂(Mn_0.985Fe_0.015)₂O_y     

Phase boundary between uniaxial and planar ferromagnets in layered perovskite manganite La2−2xSr1+2xMn2O7 (0.313⩽x⩽0.350)

We have examined magnetizations as a function of temperature and magnetic field in layered perovskite manganites La_2−2xSr_1+2xMn₂O₇ single crystals (x=0.313, 0.315, 0.318, 0.320 and 0.350) in order to determine the phase boundary between two ferromagnets (one is an uniaxial ferromagnet whose easy axis is parallel to the c-axis and the other is a planar ferromagnet whose easy axis is within the ab-plane) and following results are obtained: (i) all the present manganites exhibit magnetic transitions from a ferromagnet to a paramagnet at 76, 107, 116, 120 and 125 K for x=0.313, 0.315, 0.318, 0.320 and 0.350, respectively; (ii) for x=0.318, 0.320 and 0.350, the magnetic structure is a planar ferromagnet below Curie temperature; (iii) for x=0.313 and 0.315, the magnetic structure changes from an uniaxial to a planar ferromagnet at 66 and 85 K, respectively. From the results described above we have constructed the magnetic phase diagram of layered perovskite manganite La_2−2xSr_1+2xMn₂O₇ (0.313?x?0.350).     

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.     

Magnetic properties of transition metal substituted La0.85Ag0.15Mn1−yMyO3 compounds (M=Co, Cr and Al)

In this paper we report a systematic study of Mn-site substitution by M=Co, Cr and Al in La_0.85Ag_0.15MnO₃ series to understand the magnetic interactions between Mn and other transition metals. The long-range ferromagnetic (FM) ordering of the parent compound was significantly affected by Mn-site substitution. The measured magnetic properties of Co-doped samples have been explained on the basis of FM interactions in Mn³⁺-O-Mn⁴⁺, Co²⁺-O-Mn⁴⁺, Co³⁺-O-Mn⁴⁺ networks and simultaneous antiferromagnetic (AFM) interactions in Mn⁴⁺-O-Mn⁴⁺, Co²⁺-O-Mn³⁺ networks. The magnetic properties of Cr-doped compounds could be understood on the basis of double exchange FM interactions in Mn³⁺-O²⁻-Mn⁴⁺ networks and competing AFM in Cr³⁺-O-Mn⁴⁺, Mn⁴⁺-O-Mn⁴⁺, Cr³⁺-O-Mn³⁺ networks. However, it is found that the doping of Al ions play a role of magnetic dilution, without contributing any other competing magnetic interaction. The field variations of magnetization of all the above three series could be analysed by fitting to Brillouin function model and the effective spin contribution for FM has been determined. The measured saturation magnetization has been explained quantitatively.     

Preparation, magnetoresistance and magnetocaloric effect of two-layered perovskite La 2.5- x K 0.5+ x Mn 2 O 7+δ

Polycrystalline two-layered perovskite La_2.5-xK_0.5+xMn₂O _{7 + δ} (0 < x < 0.5) samples have been prepared by a modified sol-gel method and their magnetoresistance and magnetocaloric effects have been studied. A large deviation between the metal-insulator (MI) transition temperature (T _ρ ) and the magnetic transition temperature (T_C) is observed. Large magnetoresistance (MR) effects with Δρ/ρ of ∼40% at 12 kOe are obtained in wide temperature ranges. The maximum of the magnetic entropy change peaks at its Curie temperature (T_C), far above its MI transition temperature (T _ρ ). The large magnetic entropy change (∼1.4 J/kg.K) is obtained in the sample La_2.5-xK_0.5+xMn₂O _{7 + δ} (x = 0.35) upon 10 kOe applied magnetic field. Received 2 May 2002 / Received in final form 1st October 2002 Published online 19 December 2002 RID="a" ID="a"e-mail: wzhong@ufp.nju.edu.cn     

The effect of transition element doping on the electronic and magnetic properties of La1.4Sr1.6Mn2O7

The effect of transition element (TE=Cr, Fe, Co, Ni, Cu, Zn) doping on the electronic transport and magnetic properties in the bilayer manganite La_1.4Sr_1.6Mn₂O₇ is studied for the same dopant concentration fixed at 2%. Doping does not cause change in structure but different behavior in magnetic and transport properties. Except for Cr, all the other dopings significantly shift the magnetic transition temperature (T_C) to a lower temperature. Associated with such a decrease, the insulator-metal transition temperature (T_IM) decreases and the peak resistivity (ρ_p) at T_IM increases. Cr doping enhances T_C and T_IM as well as decreases ρ_p. Fe doping apparently has a stronger effect than Co and Ni doping. It is also indicated that Cu doping causes an anomalously large increase in ρ_p. These behaviors are compared with those observed in other bilayer manganites such as La_1.2Sr_1.8Mn₂O₇ as well as in La_0.7Ca_0.3Mn_1−xTE_xO₃.     

Charge ordering-disordering in the Th-doped CaMnO3

The structural transitions that appear in the manganites Ca_1-xTh_xMnO₃ versus temperature are studied in connection with their magnetic and transport properties, and compared to those of the Ca_1-xLn_xMnO₃ manganites. An orthorhombic to monoclinic transition is observed for low x values (;this structural distortion, also observed for Ln-doped oxides, is related to the magnetoresistance properties. For higher x values (), modulated commensurate and incommensurate phases are obtained at low temperature, with , b =2 a p and , which are related to Mn³⁺/Mn⁴⁺ charge ordering (CO) phenomena. T values, determined from electron diffraction, are in agreement with those determined from the M ( T ) curves. The low temperature electron microscopy shows that the CO in those oxides is more complex than in Ln-doped manganites. In particular, the destabilisation of CO and consequently of the antiferromagnetic interactions is evidenced as the thorium content increases which may explain the appearance of a spin-glass like behavior for higher x values not seen for Ca_1-xSm_xMnO₃ phases . Received 2 November 1998