Magnetic interaction in Mg, Ti, Nb doped manganites

An effect of Mn substitution with Me=Mg²⁺, Ti⁴⁺, Nb⁵⁺ in manganites has been investigated by preparing La_0.7Sr_0.3(Mn_1-xMe_x)O₃ and La_1-xSr_x(Mn_{1 - x/2}Nb_x/2)O₃ series. It was established that substitution of manganese with magnesium up to x = 0.16 leads to a collapse of a long-range ferromagnetic order whereas La_0.7Sr_0.3(Mn ^{3 +} _0.85Nb ^{5 +} _0.15)O₃ is ferromagnet with T _C = 123 K and exhibits a large magnetoresistance below Curie point despite an absence of four-valent manganese. Hypothetical magnetic phase diagrams are constructed for La_0.7Sr_0.3(Mn_1-xMe_x)O₃ and La_1-xSr_x(Mn_{1 - x/2}Nb_x/2)O₃. Our results show that Mn³⁺-O-Mn³⁺ exchange interaction is ferromagnetic in the orbitally disordered manganites as well as an increase of Mn⁴⁺ content above 50% from a total amount of manganese ions leads to formation of a spin glass state due to a competition between antiferromagnetic Mn⁴⁺-O-Mn⁴⁺ and ferromagnetic Mn³⁺-O-Mn⁴⁺(Mn³⁺) superexchange interactions. Received 24 January 2002 Published online 9 July 2002     

On the ferromagnetic perovskite with potential GMR properties: The manganite La1−x K x MnO3

We investigate structural features (cell distortions), magnetic and electric properties versus temperature for La_1-x K _x MnO₃ (0.05 < x < 0.2) perovskites. All the phases crystallize in a rhomboedral symmetry (R3c) and are ferromagnetic. Curie temperatures are strongly dependent of x, with a maximum around 308 K for La_0.8K_0.2MnO₃. A sharp decrease of the resistivity is observed just below the Curie temperature, accompanied by a very steep increase of the spontaneous magnetization, characteristic of a conventional Brillouin type curve. The average magnetic moment of Mn is about 88 e.m.u/g at 5 K for the composition La_0.8K_0.2MnO₃. The transition from ferromagnetic-metallic to paramagnetic-semiconducting states is explained from the suggested distribution of the cations (La³⁺ _1-x K⁺ _x )_A(Mn⁴⁺ _1-2x Mn⁴⁺ _2x )_BO₃ by the double exchange of Mn³⁺-Mn⁴⁺ pairs at the B-sublattice. Preliminary magnetoresistance measurements on bulk ceramic samples display an MR effect of the same amplitude as in the case of the alkaline earth substituted La manganites.     

Tuning the magnetocaloric properties of La0.7Ca0.3MnO3 manganites through Ni-doping

The effect of Ni²⁺ doping on the magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃ manganites synthesized via the auto-combustion method is reported. The aim of studying Ni²⁺-substituted La_0.7Ca_0.3Mn_1 ? xNi_xO₃ ($x=0,0.02,0.07$, and 0.1) manganites was to explore the possibility of increasing the operating temperature range for the magnetocaloric effect through tuning of the magnetic transition temperature. X-ray diffraction analysis confirmed the phase purity of the synthesized samples. The substitution of Mn³⁺ ions by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice was also corroborated through this technique. The dependence of the magnetization on the temperature reveals that all the compositions exhibit a well-defined ferromagnetic to paramagnetic transition near the Curie temperature. A systematic decrease in the values of the Curie temperature is clearly observed upon Ni²⁺ doping. Probably the replacement of Mn³⁺ by Ni²⁺ ions in the La_0.7Ca_0.3MnO₃ lattice weakens the Mn³⁺–O–Mn⁴⁺ double exchange interaction, which leads to a decrease in the transition temperature and the magnetic moment in the samples. By using Arrott plots, it was found that the phase transition from ferromagnetic to paramagnetic is second order. The maximum magnetic entropy changes observed for the $x=0,0.02,0.07$, and 0.1 composites was 0.85, 0.77, 0.63, and 0.59 J/kg?K, respectively, under a magnetic field of 1.5 T. In general, it was verified that the magnetic entropy change achieved for La_0.7Ca_0.3Mn_1 ? xNi_xO₃ manganites synthesized via the auto-combustion method is higher than those reported for other manganites with comparable Ni²⁺-doping levels synthesized via standard solid state reaction. The addition of Ni²⁺ increases the value of the relative cooling power as compared to that of the parent compound. The highest value of this parameter (～60 J/kg) is found for a Ni-doping level of 2% around 230 K in a field of 1.5 T.     

Cation disorder and size effects on the magnetic transition in Ba-containing ferromagnetic manganites

The results of ⁵⁵Mn NMR, dc magnetization, and ac susceptibility studies are presented for La_0.7Ca_0.15Ba_0.15MnO₃, La_0.7Sr_0.15Ba_0.15MnO₃, and La_0.7Ba_0.3MnO₃ ferromagnetic manganites. While is a function of the mean radius of the La and alkaline-earth ions and the cation disorder, the form of the temperature dependence of the magnetic moment may be expressed as function of only. The phase transition is continuous for all three compounds. Received 5 March 1999     

Relationship between the structural distortion and the Mn electronic state in La1−xCaxMnO3: a Mn K‐edge XANES study

A theoretical study of the X‐ray absorption near‐edge structure (XANES) spectra at the Mn K‐edge in the La_1?xCa_xMnO₃ series is reported. The relationship between the edge shift, the Ca–La substitution and the distortion of the MnO₆ octahedra in these systems has been studied. It is shown that, by correctly considering these effects simultaneously, the experimental XANES data are consistent with the presence of two different Mn local environments in the intermediate La_1?xCa_xMnO₃ compounds. By taking into account the energy shift associated with the modification of the MnO₆ distortion as Ca substitutes for La, it is possible to reproduce the XANES spectra of the intermediate‐doped compounds starting from the experimental spectra of the end‐members LaMnO₃ and CaMnO₃. These results point out the need to re‐examine the conclusions derived in the past from the simple analysis of the Mn K‐edge XANES edge‐shift in these materials. In particular, it is shown that the modification of the Mn K‐edge absorption through the La_1?xCa_xMnO₃ series is well reproduced by considering the simultaneous presence of both distorted and undistorted octahedra and, consequently, that the existence of charge‐ordering phenomena cannot be ruled out from the XANES data.     

Magnetocaloric properties of La0.7Ca0.3MnO3 manganites with 16O → 18O isotopic substitution

This paper reports on a study of the effect of isotopic ¹⁶O → ¹⁸O oxygen substitution on the heat capacity and magnetocaloric properties of the La_0.7Ca_0.3MnO₃ manganite. Direct measurements of the magnetocaloric effect have demonstrated that, in La_0.7Ca_0.3MnO₃, the effect reaches a fairly large magnitude, but its temperature width is rather small. The ¹⁶O ar ¹⁸O isotopic substitution shifts the temperature of the maximum of the effect toward lower temperatures while leaving its magnitude practically unchanged. The magnetocaloric effect in the La_0.7Ca_0.3Mn¹⁶O₃ + La_0.7Ca_0.3Mn¹⁸O₃ sandwich structure has been measured by the direct method. It has been shown that fabrication of a sandwich from materials with close temperatures of the maxima of the magnetocaloric effect permits increasing the relative cooling power (RCP) compared with that of the starting materials.     

Size effect in nanocrystalline manganites La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript><Emphasis Type="Italic">A</Emphasis><Subscript>x</Subscript>MnO<Subscript>3</Subscript> (<Emphasis Type="Italic">A</Emphasis>=Ag,Sr)

Nanocrystalline samples of the manganites La_0.9Ag_0.1MnO₃, La_0.7Ag_0.3MnO₃, and La_0.7Sr_0.3MnO₃ were synthesized through pyrolysis and isothermally annealed. The atomic, subatomic, and magnetic structures of these manganites were studied using magnetic, x-ray, and neutron diffraction measurements. Increasing the annealing temperature from 600 to 1200°C coarsens the grains from 30–40 to 600–700 nm in size. All the samples studied have rhombohedral structure and are ferromagnets. The Curie temperature decreases for the samples doped by silver and increases for the samples doped by strontium as the anneal temperature is increased. The magnetization of the Mn ions increases with nanoparticle size in all the three systems, which indicates the presence of a size effect.     

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.     

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.     

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.     

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.     

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.     

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.     

X-ray emission studies of evolution of the electron and spin structures of Mn in mixed manganites Ln1 ? xSrxMnO3 (Ln = La, Sm, and Ce)

The chemical shift DE_Kb1 \Delta E_{K_{\beta 1} } and the exchange splitting ΔE _split of the emission X-ray Mn K _β1 line in mixed manganites Ln _{1 − x} Sr _x MnO₃ (Ln = La, Sm, and Ce) have been systematically studied for the first time. It has been found that DE_Kb1 \Delta E_{K_{\beta 1} } and ΔE _split are almost the same in the range x < 0.4–0.5, as is the case in Mn₂O₃, and then they decrease relatively quickly to the values characteristic of MnO₂. It has been assumed that such a behavior corresponds to the model where in the region of hole doping (x < 0.5), the ground state is a mixture of configurations Mn³⁺ 3d ⁴ and $3d^4 \underset{\raise0.3em\hbox{$3d^4 \underset{\raise0.3em\hbox{, so that the second configuration fraction increases with x. At high values of x, the configuration Mn⁴⁺ 3d ³ should be taken into account; the contribution of this configuration increases with increasing degree of doping, and it becomes dominant at x = 1. In all cases, the manganese state is high-spin.     

Effect of multielement doping on low-field magnetotransport in La0.7−xMmxCa0.3MnO3 (0.0?x?0.45) manganite

We report the synthesis, structure and low-field magnetotransport properties of Mischmetal (Mm)-doped La_0.7−xMm_xCa_0.3MnO₃ (0?x?0.45) manganite. Mischmetal—Mm—is a natural mixture of rare earth elements La, Ce, Pr and Nd with ∼28%, 50%, 6% and 16% composition, respectively. All the samples crystallize in orthorhombic structure. Increasing x (Mm), corresponding to decreasing the La-site average ionic radii (〈r_A〉) hence increasing the size mismatch (i.e. variance σ²), results in strong suppression of ferromagnetism (T_C) and the associated metallicity (T_IM). It may be pointed out that Mm (La, Ce, Pr and Nd) substitution has been done to create two effects. First, creation of multivalence of Mn (2+, 3+ and 4+) via Ce substitution and second to create higher degree of disorder due to size difference brought in not only by Ce but also by Pr and Nd. Evidences and arguments based on XPS analysis suggest that multivalent ions La, Mm and Ca, and the resulting presence of Mn²⁺, Mn³⁺ and Mn⁴⁺, causes the simultaneous operation of ferromagnetism-double exchange (Mn²⁺/Mn³⁺ and Mn³⁺/Mn⁴⁺) and antiferromagnetic-superexchange (Mn³⁺/Mn³⁺ and Mn²⁺/Mn²⁺) interaction. In addition, Mm doping also creates inhomogenities at La—as well as Mn—site due to size and valency difference. A curiously huge magnetoresistance as high as ∼63% for x=0.35, under a moderate magnetic field of ∼10 kOe has been observed and even at low magnetic field of ∼3 kOe MR is ∼30%. The competing double exchange and superexchange coupled with inhomogenities are the most likely cause for the occurrence of large ∼63% CMR in the Mm-doped LCMO.     

Room temperature magnetoresistance in Ln2/3A1/3MnO3 manganites

The investigation of the manganites La_2/3−xPr_xSr_1/3MnO₃, La_2/3Sr_1/3−xCa_xMnO₃ and La_2/3+xCa_1/3−2xAg_xMnO₃, which all exhibit Mn³⁺:Mn⁴⁺=2, shows that it is possible to reach high magnetoresistance at room temperature, up to 21% under 1.2 T. These materials are compared to La_5/6Ag_1/6MnO₃ which corresponds to the same Mn³⁺:Mn⁴⁺ ratio and exhibits a magnetoresistance of 25% in this field. An interesting feature deals with the value of the insulator-metal transition temperature T_IM, often higher than T_C, especially for Ag-based compounds. It is suggested that the latter results either from a better oxygenation of the surface of the grains or from a migration of silver toward the surface.     

Magnetic studies of colossal magnetoresistance perovskites on macroscopic,mesoscopic and microscopic length scales

We have investigated magnetic correlations in various CMR manganites on macroscopic, mesoscopic and microscopic length scales by carrying out DC magnetization, neutron depolarization, and neutron diffraction measurements. We present here the effect of substituting Mn with Fe and La with Dy in the ferromagnetic La_0.7−xCa_xMnO₃ (x ∼ 0.3–0.33) compounds. Neutron diffraction has been used in order to characterize the long-range magnetic order and its gradual suppression by the substitution. Neutron depolarization study has been carried out in order to bridge the gap in our understanding regarding the nature of magnetic correlation obtained from the macroscopic and microscopic measurements. In particular, our study on La_0.67Ca_0.33Mn_0.9Fe_0.1O₃ has established the fact that a true double exchange mediated spin-glass is insulating. In another study of La-site ionic size effect and its disorder in (La_1−x Dy _x )_0.7Ca_0.3MnO₃, we have investigated the evolution of the length scale of magnetic ordering with a possible microscopic explanation and the results have been compared with that for the light rare earth substituted compounds.     

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,microstructure, the complex nature of the magnetic state of lanthanum manganite weakly doped by bismuth

Structural, magnetic, and resonance studies of Bi _x La_1–x MnO₃ are performed. Nanopowders of weakly doped compounds (x = 0.0–0.1) with particle sizes of ≤40 nm are prepared using the sol–gel technique. Nanopowder sintering under the same conditions leads to a sharp increase in the mean granule size with increasing Bi concentration. The 55Mn NMR signal of manganites prepared via solid synthesis corresponds to rapid exchange Mn⁴⁺ ? Mn³⁺. Measurements of the magnetic susceptibility reveal an inhomogeneity in the ferromagnetic state of the Bi _x La_1–x MnO₃ system.     

X-ray photoelectron spectroscopy study of the electronic structure of La<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3+δ</Subscript> solid solutions

The electronic structure of La_1–x Ga _x MnO_3+δ. solid solutions is studied by X-ray photoelectron spectroscopy (XPS). The valence state of the manganese is estimated by various methods: by analyzing the difference in the binding energies of the Mn2p_3/2 and O1s electronic levels, analyzing exchange splitting in the spectrum of Mn3s, and from the dependence of the binding energy of the XPS spectrum of Mn2p_3/2 on the calcium concentration. The state of oxidation of the manganese in the compositions containing calcium lies between Mn³⁺ and Mn⁴⁺. The efficacies of these methods are compared. A correlation is found between the type of crystalline structure of La_1–x Ga _x MnO_3+δ. (0 ≤ x < 1) and the binding energy of the Mn2p_3/2 peak. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 419–427, May–June, 2009.