Electric current-induced giant electroresistance in epitaxial La0.67Sr0.33MnO3 thin films

The electronic transport behavior of La_0.67Sr_0.33MnO₃ epitaxial thin films with different thicknesses has been investigated under various applied DC currents. The 20 and 70 nm thick films show a giant negative electroresistance (ER). In contrast, the films with 100 nm thickness show unusual giant positive ER, which can reach 30% with the current density of 1.8×10⁸ A/cm² at room temperature. It is interesting that the electric current can also change the magnetoresistance of the films. The results were explained by considering the spin polarized current induced increase of ferromagnetic metallic phase and current-induced lattice distortion via electron wind force under high current density.     

Magnetization reversal in Gd0.67Ca0.33MnO3: Comparison between epitaxial thin films and bulk

Rare-earth-based manganites ABO₃ may present interesting properties when the lanthanide (A-site) and/or the manganese (B-site) are partially substituted by divalent elements. Heavy lanthanides are particularly appealing because of the expected interplay between the intrinsic magnetic properties of the rare-earth element (Ln) and those of the ferromagnetic manganese sublattice. As such, a spin reorientation has been observed during magnetization-versus-temperature cycles due to a negative exchange interaction between Mn and Ln. We present herein high-quality epitaxial thin films (∼200 nm thick) of Gd_0.67Ca_0.33MnO₃ deposited onto (1 0 0) SrTiO₃ substrates by pulsed-laser deposition. Enhanced properties were observed in comparison with bulk samples. The magnetic transition temperature T_c of the as-grown films is much higher than the corresponding bulk values. Most interesting, magnetization measurements performed under small applied fields, exhibit magnetization reversals below T_c, no matter whether the film is field-cooled (FC) or zero-field-cooled (ZFC). The reversal mechanism is discussed in terms of a negative exchange f-d interaction and magnetic anisotropy, this latter enhanced by strain effects induced by the lattice mismatch between the film and the substrate.     

Double-peak resistivity transport properties of La0.67Ca0.33MnO3 ceramics

Polycrystalline samples of La_0.67Ca_0.33MnO₃ were prepared by solid-state reactions by varying the pelletization force and the sintering temperature. Lowering the sintering temperature gave rise to smaller grains and increased the overall resistivity of the ceramic. Partial melting was observed in the ceramics sintered at higher temperatures (1400-1500 °C). Additionally, these ceramics showed two distinct resistivity peaks. The resistivity peak near the magnetic transition (T_C) was sharp, whereas the second peak was a broad one observed below T_C.     

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.     

Epitaxial growth La0.67Ca0.33MnO3 thin film by radio frequency sputtering method

Perfect epitaxial growth of La_0.67Ca_0.33MnO₃ (LCMO) thin film has been achieved on (1 0 0) LaAlO₃ (LAO) single crystal substrate by radio frequency sputtering method. X-ray diffraction (XRD) and electron diffraction analysis indicates that La_0.67Ca_0.33MnO₃ film grows epitaxially on LaAlO₃ along [1 0 0] direction of the substrate. The resistivity variation with temperature of the film shows a sharp metal to semiconductor transition peak around 253 K, which is close to that of the target. The magnetoresistance (MR) also reveals high quality epitaxy film characteristic at low temperatures and near the metal to semiconductor transition temperature.     

Hydrogen annealing effects on polycrystalline La0.67Ba0.33MnO3 compound

Upon annealing polycrystalline La_0.67Ba_0.33MnO₃ bulk samples in flowing 95%Ar:5%H₂ mixed gas at 700 °C for different time, the insulator–metal transition temperature, _TP$T_{\mathrm{P}}$ and the amplitude of AC magnetic susceptibility were decreased first, then increased, finally decreased again. While the resistivity was increased monotonically. This anomalous behavior was explained by the combinational effects of oxygen loss and Ba ion vacancies caused by the segregation of Ba ion related impurity phase.     

Electrical transport and magnetic properties of La2/3Ca1/3MnO3/SiO2 composites

The influence of SiO₂ on the electrical transport properties of LCMO/SiO₂ composites with different SiO₂ contents x is investigated, where LCMO represents La_2/3Ca_1/3MnO₃. Results show that the SiO₂ phase not only shifts the metal–insulator transition temperature (T_p) to a high temperature range, but also has an effect on the magnetoresistance (MR) of the composites. The temperature dependence of resistivity indicates that the T_p of the composites is obviously higher than that of pure LCMO, and that the peak resistivity ρ_max of the composites is lower than that of pure LCMO. In the SiO₂ content x∼0.02, the T_P is the highest and ρ_max becomes the lowest. The experimental observation is discussed on the basis of the analysis of scanning electron microscopy (SEM) images and X-ray diffraction (XRD) patterns. Compared with pure LCMO, a possible interpretation is presented by considering the influence of SiO₂ on the coupling between ferromagnetic (FM) domains of LCMO.     

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.     

Investigation of FIB irradiation damage in La0.7Sr0.3MnO3 thin films

In this work we analyse systematically how morphological and magnetotransport properties of manganite thin films are affected by the damage induced by focused ion beam (FIB) irradiation. We irradiate different areas of the same sample with doses ranging from 5×10¹² to 3×10¹⁷ ions/cm² and we find that the film becomes swollen for doses up to 10¹⁶ ions/cm² and is eventually eroded by ion milling for further irradiation. On the other hand, transport properties are much more sensitive to FIB irradiation: the metal–insulator transition temperature is found to decrease monotonically with increasing doses up to 1.8×10¹³ ions/cm². At doses higher than 5.6×10¹³ ions/cm² the metallic state is completely suppressed and likely, also ferromagnetism.     

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.     

Growth of single-phase c-axis aligned La1.2Ca1.8Mn2O7 films on SrTiO3 (001)

We report the growth of single phase, c-axis aligned thin films of La_1.2Ca_1.8Mn₂O₇ on SrTiO₃ (001) substrates using a controlled pulsed laser deposition method. In this method, constraint of epitaxy is utilized to stabilize the Ruddlesdon-Popper (RP) phase of La_1.2Ca_1.8Mn₂O₇. Oxygen ambient pressure and the rate of deposition play a very important role in influencing the epitaxial growth as well as maintaining phase purity of the material. The oxygen pressure inside the deposition chamber was very precisely controlled and varied during the layer-by-layer growth of the film. Films, prepared by our method, show excellent electrical and magnetic characteristics with a sharp metal-insulator transition at T_M-I=90 K, closely followed by a magnetic transition at T_C=91 K.     

On the coexistence of spin and lattice polarons in the La0.67−xEuxCa0.33MnO3 CMR system

The electrical and magnetic transport properties of the La_0.67−xEu_xCa_0.33MnO₃ system exhibit lowering of insulator to metal and paramagnetic to ferromagnetic transition temperature (T_C) with the increase of Eu concentration in addition to possessing CMR property. The temperature variation of electrical resistivity and magnetic susceptibility for x=0.21 is found to have two distinct regions in the paramagnetic state for T>T_P; one with the localization of lattice polaron in the high-temperature region (T>1.5T_P) satisfying the dynamics of variable range hopping (VRH) model and the other being the combination of the spin and lattice polarons in the region T_P<T<1.5T_P. The resistivity variation with temperature and magnetic field, the cusp in the resistivity peak and CMR phenomenon are interpreted in terms of coexistence of spin and lattice small polarons in the intermediate region (T_P<T<1.5T_P). The spin polaron energy in the La_0.46Eu_0.21Ca_0.33MnO₃ system is estimated to be 106.73±0.90 meV and this energy decreases with the increase of external magnetic field. The MR ratio is maximal with a value of 99.99% around the transition temperature and this maximum persists till T→0 K, at the field of 8 T.     

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.     

Dependence of magnetic anisotropy of the La0.67Ca0.33MnO3 films on substrate and film thickness

Strain in the La_0.67Ca_0.33MnO₃ films has been tuned by varying substrate and film thickness, and its effects on magnetic anisotropy are studied based on the measurements of isothermal magnetization. Measuring the strain in the films by the out-of-plane lattice parameter (c), we found a strong dependence of the magnetic anisotropy constant (Ku) on strain. Ku decreases linearly from ∼−1.1×10⁶ erg/cm³ for c=0.763 nm to 1.2×10⁶ erg/cm³ for c=0.776 nm, corresponding to a change from tensile strain to compressive strain. Positive Ku signifies a uniaxial anisotropy with the easy axis perpendicular to the film plane, while negative Ku demonstrates an anisotropy of the easy plane character. Smaller or larger c leads a decrease or increase in Ku, which indicates the presence of other effects in addition to those associated with strain. Three distinctive processes for the magnetization are observed along the hard magnetic axis of the films on (001)SrTiO₃, suggesting a possibility of strain relaxation even in ultra-thin films.     

Large magnetoresistance induced by surface ferromagnetism in A-type antiferromagnetic La0.4Sr0.6MnO3 nanoparticles

Grain size effects on magnetic and transport properties for heavily Sr-doped A-type antiferromagnetic La_0.4Sr_0.6MnO₃ ceramics were studied. It was observed that with decrease in grain size, surface ferromagnetism could be introduced due to bond-breaking at surfaces. With decrease in grain size, the surface ferromagnetism was enhanced, and the phase transition order distinguished from the Arrott plot was a second one. The surface-induced ferromagnetism was insulating as judged from transport properties. With decrease in grain size, magnetoresistance was largely improved for both high magnetic and low magnetic fields. Under a 500 Oe magnetic field, the magnetoresistance is improved from 0.2%, 0.1%, 0.03% and 0.02% for the sample with grain size of 150 nm at 10, 100, 200 and 300 K, respectively, to 3%, 2.3%, 0.43% and 0.12% for the sample with grain size of 20 nm at 10, 100, 200 and 300 K. It was interesting to find that large magnetoresistance could be induced due to the surface ferromagnetism in A-type antiferromagnetic La_0.4Sr_0.6MnO₃ nanoparticles, which suggested that it was possible to search for manganites with relatively high low-field magnetoresistance in nanostructured A-type antiferromagnetic materials.     

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.     

The current-induced effect on the Jahn-Teller distortion in the La0.5Ca0.5MnO3 manganite

The influence of dc current on the resistivity ρ and the Young's modulus E of La_0.5Ca_0.5MnO₃ compound has been investigated by means of an in situ measuring method. At low temperatures, both the resistivity ρ and the relative modulus ΔE increase with the current. A relaxation behavior of ρ to the higher resistive state is observed at a fixed temperature and a constant current. After storing the sample for a few days, ρ decreases with the current, accompanying a slight drop of ΔE at low temperatures. Current-induced effects on ρ and ΔE are interpreted according to the current-induced interwinning of Mn³⁺O₆ octahedral distortion modes between Q₂- and Q₃-types, which is suggested to contribute to the variation of the resistivity.     

Cr-doping effect on the structural, magnetic, transport properties and Raman spectroscopy of La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 perovskites

A series of the double-doping samples La_(2+x)/3Sr_(1−4x)/3Mn_1−xCr_xO₃ (0?x?0.25) with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 have been fabricated. The structural, magnetic, transport properties and Raman spectroscopy have been investigated, and no apparent crystal structure change is introduced by Cr doping up to x=0.25. But the Curie temperature T_C and metal-insulator transition temperature T_MI are strongly affected by Cr substitution. The room temperature Raman spectra start exhibiting some new features following the increasing concentration of Cr substitutions. Moreover, it is worth noting that the frequency of the A_1g phonon mode can also be well correlated with the A-site mismatch effect (σ²), which is influenced mainly by the variety of the Sr content.     

Effects of doping Na on the structure and physical properties of La2/3Ca1/3MnO3

Effects of doping Na on the structure, electrical and magnetic properties of La_2/3Ca_1/3MnO₃ are investigated. A structural phase transition from orthorhombic to rhombohedral structure takes place at y=0.375. All samples show metal-insulator (M-I) transition at the transition temperature and undergo the transition from paramagnetism to ferromagnetism at the Curie temperature T_C. and T_C increase monotonically with increasing Na content. However the Na-doped samples have a shoulder in their electrical transport curves found below and shows a widened magnetic transition process. On the other hand, intrinsic colossal magnetoresistance (CMR) peaks are observed in all the samples, but samples with y around 0.25 show two MR peaks which can be attributed to magnetic inhomogeneity induced by the doped Na⁺ ions. Here we propose a method to broaden the CMR peak of perovskite manganite, which is beneficial for practical applications.     

Study of the magnetization and transport properties of the La(2+x)/3Sr(1−x)/3Mn1−xCrxO3 (0≤x≤0.2) system

The samples with the Mn³⁺/Mn⁴⁺ ratio fixed at 2:1 La_(2+x)/3Sr_(1−x)/3Mn_1−xCr_xO₃ (0≤x≤0.20) have been prepared. The magnetic, electrical transport, and magnetoresistance properties have been investigated. Remarkable transport and colossal magnetoresistance (CMR) effect, as well as cluster glass (CG) behaviors have been clearly observed in the samples studied. It was found that the Curie temperature T_c and insulator−metal transition temperature T_p1 are strongly affected by Cr substitution. The experiment observations are discussed by taking into account the variety of tolerance factors t; the effects of A-site radius 〈r_A〉 and the A-site mismatch effect (σ²).