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).     

Investigation of the electrical and magnetic properties of electron-doped Ruddlesden-Popper phases, CaO(Pr0.08Ca0.92MnO3)n (n=1, 2, 3 and ∞)

The electrical and magnetic properties of Pr^3±-doped Ruddlesden-Popper manganates with the formula, CaO(Pr_0.08Ca_0.92MnO₃)_n (n=1,2,3 and ∞) have been investigated. The electrical conductivity of the samples increases with the number of perovksite slabs sandwiched between the rock-salt-like CaO layers. Magnetic susceptibility measurements show an anomalous behavior for the n=1 composition which is attributed to the near absence of ferromagnetic correlations in a two-dimensional system. The magnetic behavior of other members can, however, be understood on the basis of a ‘ferromagnetic-droplet’ model. Since the number of electrons per perovskite slab is invariant across the series, the electronic properties are readily correlated to the phase space available for exchange interactions.     

Electrical transport behavior of La0.67Ca0.33MnO3/Fe3O4 composites

The influence of Fe₃O₄ contents on the electrical transport properties (resistivity and ac susceptibility) of a series of composite samples of La_0.67Ca_0.33MnO₃/Fe₃O₄ is studied. Results show that the Fe₃O₄ phase not only shifts the intrinsic insulator-metal (I-M) transition temperature T_P1 to a lower temperature, but also causes a new I-M transition at a lower temperature T_P2 (T_P2<T_P1). On the basis of an analysis by scanning electron microscopy and X-ray diffraction, we suggest that the decrease of the I-M transition temperature and the formation of the new I-M transition are caused by the segregation of a new phases related to the Fe₃O₄ at grain boundaries or surfaces of the La_0.67Ca_0.33MnO₃ grains.     

Effects of Ag addition on electrical transport and magnetic properties of La0.67Ba0.33Mn0.88Cr0.12O3

We have prepared a series of polycrystalline manganites with the nominal compositions, La_0.67Ba_0.33Mn_0.88Cr_0.12O₃/Ag_x (LBMCO/Ag_x) (x   is the mole fraction) with x=0$x=0$, 0.05, 0.1, 0.15, 0.2, 0.23, 0.27, 0.3, 0.35. The X-ray diffraction patterns show that the samples with x>0.05$x>0.05$ are two-phase composites. The Ag addition in LBMCO improves the properties of grain surfaces/boundaries and reduces the resistivity of the composites. For x=0.30$x=0.30$ sample, a minimum resistivity is obtained and a maximum room temperature magnetoresistance up to −54.5% was observed at 288 K, 1 T field. The room temperature T_C and the reduced resistivity are responsible for the enhancement of room temperature MR.     

Modified texture and high temperature transport properties of doubly substituted BaxAgyCa2.8Co4O9 thermoelectric oxide

Doubly substituted polycrystalline compound bulk samples of Ba_xAg_yCa_2.8Co₄O₉ were prepared via citrate acid sol-gel method followed by spark plasma sintering. The phase composition, orientation, texture and high temperature electrical properties were systematically investigated. The results showed that the orientation and the texture could be modified by altering ratio of Ba to Ag. The resistivity and the Seebeck coefficient of substituted samples were decreased by decreasing Ba/Ag ratio except for that of Ba_0.1Ag_0.1Ca_2.8Co₄O₉ sample with lowest electrical resistivity (7.2 mΩ cm at 973 K), moderately high Seebeck coefficient (172 μV/K at 973 K) and improved power factor (0.42 mW/mK² at 973 K).     

Large room temperature magnetoresistance in YSZ doped La0.67Ba0.33MnO3 composite

The temperature dependence of the resistivity for composite samples of (1−x)La_0.67Ba_0.33MnO₃+xYSZ(LBMO/YSZ) with different YSZ doping level of x has been investigated in a magnetic field range of 0-7000 Oe, where the YSZ represents yttria-stabilized zirconia (8 mol% Y₂O₃+92 mol% ZrO₂). With increasing YSZ doping level, the range of 0-10%, the metal-insulator transition temperature (T_P) decreases. However, the resistivity, specially the low temperature resistivity, increases. Results also show that the YSZ doping level has an important effect on a low field magnetoresistance (LFMR). In the magnetic field of 7000 Oe, a room temperature magnetoresistance value of 20% was observed for the composite with a YSZ doping level of 2%, which is encouraging for potential application of CMR materials at room temperature and low field.     

Enhancement of magnetoresistances at room temperature in YSZ doping La0.67Sr0.33MnO3 system

The temperature dependence of the resistance of composite samples (1−x)La_0.67Sr_0.33MnO₃+xYSZ with different YSZ doping level x was investigated at magnetic fields 0-3 T, where YSZ represents yttria-stabilized zirconia. Results show that the YSZ dopant does not only adjust the metal-insulator transition temperature, but also increases the magnetoresistance effect. With increase of YSZ doping level for the range of x<2%, the metal-insulator transition temperature values T_P of the composites decrease, but T_P increases with increase of x further for the range of x>2%. Meanwhile, in the YSZ-doped composites, a broad metal-insulator transition temperature region was found at zero and low magnetic field, which results in an obvious enhanced magnetoresistance in the temperature range 10-350 K. Specially, a larger magnetoresistance value was observed at room temperature at 3 T, which is encouraging with regard to the potential application of magnetoresistance materials.     

Magnetoresistance and transport properties of different impurity doped La0.67Ca0.33MnO3 composite

An enhanced magnetoresistance and a two-fold effect result from impurity dopant were observed in composites of La_0.67Ca_0.33MnO₃/YSZ and La_0.67Ca_0.33MnO₃/Fe₃O₄. Where YSZ represents yttria-stabilized zirconia and the doping level of both YSZ and Fe₃O₄ is 1 mol%. Different electrical and magnetic transport properties, in particular a lower field magnetization behavior, were observed between pure La_0.67Ca_0.33MnO₃ and the impurity doped La_0.67Ca_0.33MnO₃ composites. Compared with pure La_0.67Ca_0.33MnO₃, a possible interpretation is presented by considering the influences of YSZ and Fe₃O₄ on the structure of grain boundaries and/or surfaces of La_0.67Ca_0.33MnO₃grains.     

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.     

Large enhancement of room temperature magnetoresistance in Ag-added La0.67(Ca0.65Ba0.35)0.33MnO3

The electrical and magnetoresistant properties of La_0.67(Ca_0.65Ba_0.35)_0.33MnO₃/Ag_x (abbreviated by LCBMO/Ag_x) have been studied. The results show that Ag addition causes a decrease of resistivity dramatically and especially induces a large enhancement of room temperature magnetoresistance (MR). The room temperature MR ratio for x=0.27 sample in 10 kOe magnetic field is 41%, almost 20 times larger than that for x=0 sample. This enhancement is related to that the Curie temperature (T_c) of the sample is near room temperature, as well as the significant reduction of resistivity. The good fits of experimental results for x=0.27 sample to Brillouin function indicate that the MR behavior in the Ag added LCBMO is induced by the spin-dependent hopping of the electrons between the spin clusters, which is an intrinsic property of the CMR materials.     

Electrical conductivity and low field magnetoresistance in polycrystalline La1−xKxMnO3 pellets prepared by pyrophoric method

Electrical conductivity and magnetoresistance of a series of monovalent (K) doped La_1−xK_xMnO₃ polycrystalline pellets prepared by pyrophoric method have been reported. K doping increases the conductivity as well as the Curie temperature (T_C) of the system. Curie temperature increases from 260 to 309 K with increasing K content. Above the metal-insulator transition temperature (T>T_MI), the electrical resistivity is dominated by adiabatic polaronic model, while in the ferromagnetic region (50<T<T_MI), the resistivity is governed by several electron scattering processes. Based on a scenario that the doped manganites consist of phase separated ferromagnetic metallic and paramagnetic insulating regions, all the features of the temperature variation of the resistivity between ∼50 and 300 K are described very well by a single expression. All the K doped samples clearly display the existence of strongly field dependent resistivity minimum close to ∼30 K. Charge carrier tunneling between antiferromagnetically coupled grains explains fairly well the resistivity minimum in monovalent (K) doped lanthanum manganites. Field dependence of magnetoresistance at various temperatures below T_C is accounted fairly well by a phenomenological model based on spin polarized tunneling at the grain boundaries. The contributions from the intrinsic part arising from DE mechanism, as well as, the part originating from intergrannular spin polarized tunneling are also estimated.     

Electronic and magnetic phase transitions in (Sm0.65Sr0.35)MnO3 induced by temperature and magnetic field

Temperature (4.2–260 K) and magnetic field (0–50 kOe) dependencies of the DC electrical resistance, DC magnetization, and AC magnetic susceptibility of (Sm_0.65Sr_0.35)MnO₃ prepared from high purity components have been studied. (Sm_0.65Sr_0.35)MnO₃ undergoes a temperature-induced transition between low-temperature ferromagnetic metallic and high-temperature paramagnetic insulating-like states. A magnetic field strongly affects this transition resulting in a metallic state and “colossal” magnetoresistance in the vicinity of the metal↔insulator transition. Magnetic and electric properties of (Sm_0.65Sr_0.35)MnO₃ are different compared to those reported earlier for similar composition, which is attributable to the purity of the starting materials and/or different process of synthesis. The character of phase transformations observed in (Sm_0.65Sr_0.35)MnO₃ is compared to that reported for Gd₅(Si_xGe_4−x) intermetallic alloys with a true first order phase transition.     

Effect of Ti doping on the electrical transport and magnetic properties of layered compound Na0.8CoO2

Effect of Ti doping on the electrical transport and magnetic properties of layered Na_0.8Co_1−xTi_xO₂ compounds has been investigated. The lattice parameters a and c increase with x. A minor amount of Ti doping results in a metal-insulator transition at low temperatures. For samples with x>0.03, the variable-range hopping process dominates the transport behavior above a certain temperature. The temperature dependence of magnetization of all the samples is found to obey the Curie-Weiss law. The mechanism of the doping effect is discussed.     

Magnetic,electrical transport and electron spin resonance studies of ferromagnetic insulating manganites Nd0.85Na0.15MnO3

We have investigated the magnetic, electrical transport and electron spin resonance (ESR) properties of polycrystalline Nd_0.85Na_0.15MnO₃ prepared by sol–gel method. A ferromagnetic–paramagnetic (FM–PM) transition is observed around 110 K, which is not accompanied by a metal–insulator transition. The sample displays the complete PM state associated with the ESR spectra fitted by single Lorentzian line shape above 130 K. Below 130 K, ESR spectra become distorted and then linewidth increases rapidly, where short-range magnetic order develops and coexists with PM phase due to the inhomogeneous magnetic state. In addition, the large difference between the activation energies obtained from the resistivity and ESR parameters (peak-to-peak linewidth and line intensity) at the frame of adiabatic small polaron hopping model is pointed out for Nd_0.85Na_0.15MnO₃.     

Fe3O4 Segregation and Transport Properties of La0.67Ca0.33MnO3

Effect of Fe3O4 segregation at grain boundaries on the electrical transport and magnetic properties of La0.67Ca0.33MnO3 is investigated. The experimental results show that the Fe3O4 segregation not only shifts the paramagnetic-ferromagnetic transition temperature of La0.6TCa0.33MnO3 to a lower temperature region but also induces a new transition in a lower temperature region. Meanwhile, the transition processes observed in both the resistivity and magnetization curves are obviously widened. Compared to pure La0.67Ca0.33MnO3, we assume that the Fe3O4 segregation level at the grain boundaries can modify the electrical transport and magnetic properties of La0.67Ca0.33MnO3.     

Magnetic anisotropy in colossal magnetoresistive FeCr2S4 single crystals

The magnetic properties of spinel FeCr₂S₄ single crystals were investigated by ferromagnetic resonance (FMR). The FMR spectrum displays a single absorption line in the whole temperature range measured for both H∥(111) and H⊥(111). With decreasing temperature, the line with H∥(111) shifts to lower fields, while that with H⊥(111) shifts to higher fields. By superposing all the FMR spectra measured in different directions at 110 K, a double-peak is obtained, which clarifies the origin of the FMR double-peak in polycrystalline sample. By taking account of magnetic anisotropy and demagnetizing effect, the orientation dependence of resonance field is well fitted. It is found that the magnetic anisotropy strengthens with decreasing temperature; however, it has no evident influence on transport and colossal magnetoresistance behavior.     

ESR investigation of the spin dynamics in (Gd1−xYx)2PdSi3

We report electron-spin resonance (ESR) measurements in polycrystalline samples of (Gd_1−xY_x)₂PdSi₃. We observe the onset of a broadening of the linewidth and of a decrease of the resonance field at approximately twice the Néel temperature in the paramagnetic state. This characteristic temperature coincides with the electrical resistivity minimum. The high-temperature behavior of the linewidth is governed by a strong bottleneck effect.     

Influence of high-energy electron irradiation on the transport properties of La1-xCaxMnO3 films ($$(x \approx 1/3)$$ )

The effect of crystal lattice disorder on the conductivity and colossal magnetoresistance in La_1-xCa_xMnO₃ ( ) films has been examined. The lattice defects are introduced by irradiating the film with high-energy ( MeV) electrons with a maximal fluence of about cm^-2. This comparatively low dose of irradiation produces rather small radiation damage in the films. The number of displacements per atom (dpa) in the irradiated sample is about 10^-5. Nevertheless, this results in an appreciable increase in the film resistivity. The percentage of the resistivity increase in the ferromagnetic metallic state (below the Curie temperature ) was much greater than that observed in the insulating state (above ). At the same time irradiation has much less effect on or on the magnitude of the colossal magnetoresistance. A possible explanation of such behavior is proposed. Received 21 July 1999 and Received in final form 27 December 1999