Colossal magnetocapacitance effect in BiFeO3/La5/8Ca3/8MnO3 epitaxial films

A colossal magnetocapacitance in magnetic fields was observed near the Curie temperature T_c = 220 K of La_5/8Ca_3/8MnO₃ for the BiFeO₃/La_5/8Ca_3/8MnO₃ epitaxial film. It was found that the magnetocapacitance increases with increasing magnetic fields and reaches a maximum up to 1100% enhancement around T_c at 10 T. From the analysis of the dielectric relaxation, one can see that the behavior of relaxation time τ above T_c differs from that below T_c, and the value of τ decreases with increasing magnetic fields. This colossal magnetocapacitance effect near room temperature in BiFeO₃/La_5/8Ca_3/8MnO₃ may have potential applications in multifunctional microelectronic device.     

Electrical properties of Ag-La0.7Ca0.3MnO3

The temperature dependence of the electrical resistivity in (1 − x) La_0.7Ca_0.3MnO₃ + xAg composites has been investigated between 5 and 300 K for H = 0 and 3T. Ag addition has increased the conductivity of this system. Curie temperature (T_C) is almost independent of Ag content and is ~ 260 K for all the samples, while the metal-insulator transition temperature (T_MI) increases with increasing content of Ag. The ρ-T of all samples fit well with the phenomenological percolation approach, which is based on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions. In addition, all the samples clearly reveal the unusual low temperature resistivity minimum. Analysis of our results in terms of the model based on charge carrier tunneling between the anti-ferromagnetically coupled grains shows excellent agreement with the experiment data for both H = 0 and 3T.     

Effects of chemical stability of heterogeneous oxides on transport properties of La0.67Ca0.33MnO3

Two kinds of composites of La_0.67Ca_0.33MnO₃/ZrO₂ and La_0.67Ca_0.33MnO₃/YSZ have been investigated, in which the heterogeneous oxide YSZ represents yttria-stabilized zirconia (8 mol% Y₂O₃ + 92 mol% ZrO₂). Their transport properties are measured in a temperature range of 10-300 K and a magnetic field range of 0-3 T. With increase in ZrO₂ doping level for the range of 0-2%, the metal-insulator transition temperature, T_P, decreases, but T_P increases with the doping level increase further for higher than 2%. Meanwhile, in the composite of La_0.67Ca_0.33MnO₃/ZrO₂, besides the intrinsic metal-insulator (ferromagnetic-paramagnetic) transition, a new kink and a widen transition temperature region are observed both in the temperature dependence of resistivity and magnetization curves. Compared to pure La_0.67Ca_0.33MnO₃ and the composite of La_0.67Ca_0.33MnO₃/YSZ, we assume that the different effects between ZrO₂ and YSZ on transport behavior of La_0.67Ca_0.33MnO₃ result mainly from their different chemical stability.     

Photoconductivity in BiFeO3/La0.7Sr0.3MnO3 heterostructure

In this letter, an oxide heterostructure has been fabricated by successively growing La_0.7Sr_0.3MnO₃ (LSMO) and BiFeO₃ (BFO) layers on LaAlO₃ (100) by pulsed laser deposition. Analysis of the leakage current at different temperature demonstrated that the Poole-Frenkel dominated the leakage current mechanism. Additionally, the BiFeO₃/La_0.7Sr_0.3MnO₃ heterostructure exhibits a positive colossal magnetoresistance (MR) effect over a temperature range of 50-320 K. The maximum MR values are determined to be about 45.32% at H = 0.5 T and 28.34% at H = 0.3 T. At last, we report photoconductivity in BiFeO₃/La_0.7Sr_0.3MnO₃ film under illumination from 160 mW/cm² and 200 mW/cm² green-light source, and photoconductivities increase with the intensity of light enhanced.     

Effect of high temperature post-annealing of La0.7Sr0.3MnO3 films deposited by radio frequency magnetron sputtering on SiO2/Si substrates heated at low temperature

La_0.7Sr_0.3MnO₃ thin films were deposited on SiO₂/Si substrates by RF magnetron sputtering under different oxygen gas flow rates with a sputtering power of 100 W. During deposition, the substrate was heated at 623 K. To investigate post-annealing effects, the as-deposited La_0.7Sr_0.3MnO₃ thin films were thermal-treated at 973 K for 1 h. The effects of oxygen gas flow rate and post-annealing treatment on the physical properties of the films were systematically studied. X-ray diffraction results show that the growth orientation and crystallinity of the films were greatly affected by the oxygen gas flow rate and substrate heating during deposition. The sheet resistance of the films gradually decreased with increasing oxygen gas flow rate, while the post-annealed films showed the opposite behavior. The temperature coefficient of resistance at 300 K of La_0.7Sr_0.3MnO₃ thin films deposited at an oxygen gas flow rate of 40 sccm decreased from − 2.40%/K to − 1.73%/K after post annealing. The crystalline state of the La_0.7Sr_0.3MnO₃ thin films also affected its electrical properties.     

Broadening of the magnetic entropy change in La0.75Ca0.15Sr0.10MnO3

A broad table-like entropy change (ΔS) at room temperature has been observed in the ferromagnetic compound La_0.75Ca_0.15Sr_0.10MnO₃, which is analyzed in the concept of Landau theory and with critical exponent analysis obtained from the magnetization measurements. The change in entropy in La_0.75Ca_0.15Sr_0.10MnO₃ is discussed in the light of magnetoelastic coupling between the magnetization and the lattice distortion. Application aspects of this unusual broad magnetocaloric effect with relative cooling power of 107 J kg⁻¹ in an applied magnetic field of 1.6 T with an operating temperature range of 93 K around the room temperature are also discussed.     

Photoluminescence properties of V-doped La0.67Ca0.33Mn1−xVxO3

The optical spectra have been investigated for a prototypical double exchange ferromagnetic La_0.67Ca_0.33MnO₃ with Mn substituted by V above the paramagnetic-magnetic transition temperature T_C. The excitation spectra under the probe wavelength of λ_em = 473 nm for all samples exhibit two activation bands around 360 and 294 nm, involving an electron transfer from oxygen 2p states to the Mn d states in MnO₆ octahedra. The photoluminescence spectra at λ_ex = 290 nm have the similar spectral features for all samples. The photoluminescence spectral peaks located at 400, 473, 534, 670, 738 and 770 nm, and the corresponding photon energy is in a broad range of 3.1-1.6 eV, indicating that the PL bands could have the different origin: the self-trapped excitons localized on MnO₆ octahedra; the interband transition between the O 2p and Mn 3d bands; the transition between the 3d electron states of Mn ions. So, it can be clearly seen that the electronic behavior above T_C is very complicated. Our results suggest that the charge transfer from O 2p to Mn 3d has the important effects on the electronic structure, and it not only contributes to the optical transition but is helpful and even important to understand the electric, magnetic and thermal properties etc. due to the strong correlation among charge, spin and lattice in perovskite manganites.     

Magnetic and transport properties of La0.3Ca0.7Mn0.9T0.1O3 (T = Cr, Fe, and W)

We have carried out structural, magnetic and magneto transport measurements of the electron-doped manganite La_0.3Ca_0.7MnO₃ substituted with 10% of Cr, Fe and W on the Mn site. The substitution by Cr, Fe and W suppresses the charge order transition present at 260 K in the parent compound. All the samples show a semiconducting behavior. Whereas the parent compound does not show any magneto resistance (MR) even in a field of 14 T, a maximum MR of 6% in 5 T at 25 K is observed for the Cr substituted sample that is attributed to a spin-cluster glass like states induced by Cr. The Fe and W substituted samples showed a MR of 1.5 and 3%, respectively which may be attributed to a smaller number of FM domains/spin-clusters and to an increase in anti-ferromagnetic interaction.     

Magnetocaloric effect in La<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript> for <Emphasis Type="Italic">x</Emphasis> = 0.3, 0.35, and 0.4

We present systematic studies of the magnetocaloric properties of the polycrystalline La_1−x Ca _x MnO₃ system for x = 0.3, 0.35, and 0.4 near a second-order phase transition from a ferromagnetic to a paramagnetic state. The crystal structure of the studied manganites was shown to be in good agreement with previous reports. The value of the magnetocaloric effect has been determined from the measurement of magnetization as a function of temperature and external magnetic field. The maximum entropy change detected in La_0.7Ca_0.3MnO₃ at a field of 2 T reaches 8 J/kg K which exceeds that of gadolinium. In all studied samples, the paramagnetic–ferromagnetic transition is very narrow but no hysteresis is observed and the transitions are identified as second-order ones. The phase transition in La_0.7Ca_0.3MnO₃ appears to be almost of first-order.     

Magnetocaloric Effect in La0.7Cd0.3MnO3, La0.7Ba0.3MnO3, and Nd0.7Sr0.3MnO3

We have based on isothermal magnetization curves to study the magnetocaloric effect (MCE) in fine-grained perovskite manganites of La_0.7Cd_0.3MnO₃ (LCMO), La_0.7Ba_0.3MnO₃ (LBMO), and Nd_0.7Sr_0.3MnO₃ (NSMO) prepared by conventional solid-state reaction. Magnetic measurements were performed on a vibrating sample magnetometer, with a temperature increment of 1.0?K, and the applied field in the range of 0?C1.8?T. Under an applied field of 1.8?T, the maximum magnetic-entropy change obtained for LCMO, LBMO, and NSMO taking place at their Curie temperature are about 2.3, 2.1, and 5.1?J/(kg?K), respectively. The large entropy change in NSMO makes it suitable for magnetic-cooling applications.     

Large magnetocaloric effect in Ti-modified La0.70Sr0.30MnO3 perovskite

The effect of Ti substitution on the magnetocaloric effect of the La_0.70Sr_0.30MnO₃ perovskite was investigated. The magnetic entropy change (− ΔS_M) was deduced by two methods: a Maxwell relation and the Landau theory. The magnetocaloric data displays a large value of the magnetic entropy change (− ΔS_M) near the Curie temperature (T_C = 210 K), which increases when increasing the applied magnetic field. A good agreement is found between the experimental (− ΔS_M) and the one estimated by Landau theory. The relative cooling power values vary from 49 to 288 J kg^− 1 upon variation of the applied magnetic field at 1 and 5 T. Under 5 T, the relative cooling power value for La_0.70Sr_0.30Mn_0.90Ti_0.10O₃ is about 70% of the conventional refrigerant Gd material. As a result, the herein reported compound can be considered as a promising material in magnetic refrigeration technology.     

Giant magnetoresistance in La0.67Ca0.33MnO3 granular system with CuO addition

We report on a heterogeneous precipitation method to modify the surfaces of La_0.67Ca_0.33MnO₃ (LCMO) grains with CuO. It is shown that such a modification causes transport and magnetoresistance (MR) properties of the composites largely different from that observed in pure LCMO granular system. Especially, a significant enhancement in MR is observed near the insulator-metal transition temperature (T_IM). The maximum MR reaches as high as ∼88 and ∼90% at a low magnetic field of 0.3 T for the modified samples of LCMO/xCuO with x = 4 and 15 mol%, respectively. Compared to pure LCMO, the CuO-modified samples have a substantial decrease in resistivity (ρ) at the temperature regions apart T_IM. Furthermore, for the x = 4% sample, a considerable thermal hysteresis is observed at the same temperature region where abnormal MR effect appears. On the basis of magnetization measurement and structural analysis, a possible interpretation for the experimental observations is presented.     

Phase formation mechanism and kinetics in solid-state synthesis of undoped and calcium-doped lanthanum manganite

LaMnO_3+δ and La_0.7Ca_0.3MnO₃ were synthesized from La₂O₃(La(OH)₃), CaCO₃ and MnO₂ powder mixture with solid-state reaction technique. X-ray diffraction and thermal analysis were employed in the present study on the process of synthesizing of the two compound powders. The kinetic study on solid-state reaction between La₂O₃ and MnO₂ in the powder mixture was isothermally carried out for LaMnO_3+δ formation. The result showed that the reaction process was controlled by three-dimensional solid-ionic diffusion. Both Jander and Ginstling-Brounstein model can be used to describe the reaction kinetics satisfactorily. The relevant apparent activation energy values obtained were as great as 205 ± 11 and 189 ± 8 kJ/mol. The reaction process of La_0.7Ca_0.3MnO₃ preparation from La₂O₃, SrCO₃ and MnO₂ powder mixture was also studied using X-ray diffraction and thermal analysis. The result indicated that the following steps composed the overall reaction: the decomposition of the reactant; the formation of La_1−xCa_xMnO_3+δ; La₂O₃ and Mn₃O₄ reacted with La_1−xCa_xMnO₃ to form final La_0.7Ca_0.3MnO₃ phase. The latest step was the most time-consuming one among others in the overall reaction.     

Preparation and colossal magnetoresistance in a trilayer La0.67Sr0.33MnO3/La0.75MnO3/La0.67Sr0.33MnO3 device by dc magnetron sputtering

Epitaxial trilayer films of La_0.67Sr_0.33MnO₃ (LSMO)/La_0.75MnO₃ (L0.75MO)/La_0.67Sr_0.33MnO₃ (LSMO) have been prepared on (0 0 1) oriented LaAlO₃ substrates by dc magnetron sputtering. The structure and MR are studied. All as-deposited trilayer films exhibit a semiconductor to metal transition at temperature ranging from 116 to 185 K. The MR is also shown to be dependent on the thickness of the middle oxide layer. A maximum MR value of 32% (ΔR/R₀) has been obtained at 132 K under 0.4 T magnetic field for a LSMO (300 nm)/L0.75MO (70 nm)/LSMO (300 nm) trilayer film. The MR of trilayer film prefers to that of both LSMO and L0.75MO single layer films.     

Structural and magnetic properties of La0.85Ca0.15Mn1 − xCrxO3

Chromium (Cr) is doped at the Mn site of La_0.85Ca_0.15MnO₃ system to explore its complex ferromagnetic insulating (FMI) state. The Rietveld refinement of neutron diffraction data indicates that there is no structural change owing to Cr substitution in La_0.85Ca_0.15Mn_1 − xCr_xO₃ (0 ≤ x ≤ 0.1). Nevertheless, it strengthens the magnetic couplings and the system shifts towards enhanced ferromagnetic (FM) ordering. Doping with Cr is found to stabilise the FMI state at low temperatures. The magnetic moment of the parent compound (for x = 0) obtained from neutron diffraction data recorded at low temperature (17 K) is found to be ~ 3.53(5) μ_B and is close to the theoretically estimated value of 3.85 μ_B. This value is higher than previously reported value of 2.90 μ_B.     

Magnetocaloric properties in Ln0.67Ba0.33Mn1 − xFexO3 (Ln = La or Pr) manganites

We have investigated the magnetocaloric properties of Ln_0.67Ba_0.33Mn_1 − xFe_xO₃ (Ln = La or Pr) manganites with x = 0 and 0.05. All compounds present a maximum and large magnetocaloric effect near the Curie temperature (T_C). The associated maximum value of the magnetic entropy change, at 5 T applied change in the magnetic field, is 4.37 J.kg^− 1.K^− 1 for Pr_0.67Ba_0.33MnO₃ manganite with a T_C value of 205 K. The corresponding relative cooling power (RCP) reaches 230 J.kg^− 1. All the samples present similar RCP values that are relatively high and are promising materials to be used in ecologically friendly magnetic refrigeration technology. Iron doping reduces both T_C and ΔS_M^max and spreads the temperature working range with an almost constant RCP and can then be used to tune the working conditions of a refrigerator device.     

Microwave assisted low temperature rapid synthesis of manganite system using La0.67Ce0.03Sr0.3MnO3 mini-cavity furnace

Amorphous La_0.7Sr_0.3MnO₃ (LSMO) and La_0.7Ca_0.3MnO₃ (LCMO) precursor powders synthesized by the citrate gel method at 673 K, have been found to crystallize by microwave irradiation in just 60 s using La_0.67Ce_0.03Sr_0.3MnO₃ (Ce-LSMO) as couplant. This is the lowest temperature treatment and synthesis time so far reported in literature for the formation of manganite systems. Using ceramic route, the same amorphous samples crystallize on heat treatment only at temperatures greater than 1000 K. The microwave heating through this method is novel and has tremendous potential for accelerating the evolution of the product phase in very shorter durations, with just low temperature processing of the precursors, which cannot be realized in normal process.     

Preparation and electrical behavior study of the ceramic interconnect La0.7Ca0.3CrO3−δ with CeO2-based electrolyte Ce0.8Sm0.2O1.9

Based on the conventional interconnect La_0.7Ca_0.3CrO_3−δ, a novel ceramic interconnect for intermediate temperature solid oxide fuel cells was developed. In the air, the electrical conductivities of La_0.7Ca_0.3CrO_3−δ + 5%Ce_0.8Sm_0.2O_1.9 at 600, 700 and 800 °C were 96.7, 146.3 and 687.8 S cm⁻¹, respectively, which increased significantly as compared with La_0.7Ca_0.3CrO_3−δ under the same conditions. Similarly, in pure hydrogen, La_0.7Ca_0.3CrO_3−δ + 3%Ce_0.8Sm_0.2O_1.9 possessed the maximal electrical conductivities which were 4.2, 5.3 and 7.1 S cm⁻¹, respectively at 600, 700 and 800 °C. The crystal structures of La_0.7Ca_0.3CrO_3−δ, La_0.7Ca_0.3CrO_3−δ + 5%Ce_0.8Sm_0.2O_1.9 and La_0.7Ca_0.3CrO_3−δ + 10%Ce_0.8Sm_0.2O_1.9 were single phase with hexagonal symmetry, cubic phase plus some doped ceria impurity and orthorhombic phase plus some doped ceria impurity, respectively. The difference between the crystal structures may account for the difference between the electrical conductivities. The electrical conductivities and sinterability of La_0.7Ca_0.3CrO_3−δ were increased by introducing Ce_0.8Sm_0.2O_1.9, whereas the other properties were not influenced.     

Magneto-electrical transport in V-patterned La0.7Sr0.3MnO3 nanostructures

We investigate the electrical transport and magnetic field dependence of nano-patterned La_0.7Sr_0.3MnO₃ devices. We find that the resistivity versus temperature dependence is the same as that observed in thin films, indicating that our nano-patterning preserves the fundamental properties of the material. At temperatures below 20 K there is resistivity upturn of ~ 5 % in the smallest and thinnest device. Structures in a “V” pattern were fabricated in order to investigate domain wall resistance. We find a much smaller resistance area product as compared to previous reports observed in nanoconstrictions and also that the switching field matches that in micromagnetic simulations.     

Antiferromagnetic manganite La1/3Ca2/3MnO3 as barrier material in superconductor/insulator/ferromagnet tunnel junctions

Current transport through thin antiferromagnetic (AF) barriers of the perovskita manganite La_1/3Ca_2/3MnO₃ (LCMO) was studied with respect to its dependence on temperature and voltage. Planar-type La_2/3Ca_1/3MnO₃(~ 80 nm)/La_1/3Ca_2/3MnO₃(~ 7 nm)/YBa₂Cu₃O_7 − δ(~ 100 nm) heterojunctions were used as basic structures. The current-voltage (I-V) measurements were carried out on test junctions with a standard area of 20 × 40 µm² in a four-terminal configuration. In spite of the carefully controlled growth conditions, barriers with the same nominal thickness showed different electrical behavior varying from elastic tunneling to Mott variable range hopping (VRH) via localized states. The different transport characteristics seem to be related to intrinsic difference in microstructure as the average surface roughness of the constituent layers may already be larger than the thickness of the barrier itself.