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.     

Microstructures of YBa2Cu3O7/La0.7Ca0.3MnO3 and La0.7Ca0.3MnO3/YBa2Cu3O7 bi-layers grown on (001)LaAlO3

Epitaxial YBa₂Cu₃O₇/La_0.7Ca_0.3MnO₃ (YBCO/LCMO) bi-layers and La_0.7Ca_0.3MnO₃/YBa₂Cu₃O₇ (LCMO/YBCO) bi-layers were grown on (001)LaAlO₃ by pulsed laser deposition, and their microstructures were compared by transmission electron microscopy investigation. In the YBCO(100 nm)/LCMO(150 nm) bi-layers, the LCMO layer consists of columnar grains of ~ 17 nm in diameter and contains mixed orientation domains of [100]_c, [010]_c and [001]_c. The YBCO layer is totally c-axis oriented and the YBCO lattices are tilted − 2.5° to + 2.5° as they grew on the rough surfaces of LCMO columnar grains. For the LCMO(140 nm)/YBCO(140 nm) bi-layers, the LCMO/YBCO interface is sharp and flat. The initial 12-nm thickness of the YBCO layer is composed of c-axis oriented domains, and the upper part of YBCO layer is [100] oriented. The LCMO layer was predominantly [001]_c oriented while [100]_c-oriented domains were occasionally observed.     

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.     

Electrical properties of Pb0.97La0.02(Zr0.95Ti0.05)O3 antiferroelectric thin films on TiO2 buffer layer

Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ antiferroelectric thin films with thickness of 500 nm were successfully deposited on TiO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates via sol-gel process. Microstructure of Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was studied by X-ray diffraction analyses. The antiferroelectric nature of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was confirmed by the double hysteresis behaviors of polarization and double buffer fly response of dielectric constant versus applied voltage at room temperature. The capacitance-voltage behaviors of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films with and without TiO₂ buffer layer were studied, as a function of temperature. The temperature dependence of dielectric constant displayed a similar behavior and the Curie temperature (T_c) was 193 °C for films on both substrates. The current caused by the polarization and depolarization of polar in the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films was detected by current density-electric field measurement.     

Study of SrTiO3 thin films grown by sputtering technique for tunnel barriers in quasiparticle injection contacts

High-quality, c-axis oriented YBa₂Cu₃O_7 − x/SrTiO₃/Au (YBCO/STO/Au) planar structures were fabricated in situ by direct current/radiofrequency inverted-cylinder magnetron sputtering on (001) STO oriented substrates. The sandwich-type structures were patterned to transistor dimensions by standard ultraviolet-photolithography and Ar etching. The current transport mechanism in the very thin STO barriers (2-30 nm) was examined by measuring the tunneling G as function of temperature (T), and bias voltage (V). It was found that resonant tunneling and hopping via a small number of localized states (LS) are responsible for electronic conduction in the insulating material. Elastic tunneling was observed for the case of a nominal 2 nm thick STO-barrier with an energy gap Δ ≈ 20 meV in the (001) direction of YBCO. On the other hand, inelastic hopping transport via n-LS dominated for STO barrier thickness d > 2 nm. G of the lowest-order hopping channel (hopping via two LS) exhibits the characteristic T and V dependences: G₂^hop(T) ∝ T^4/3, G₂^hop(V) ∝ V^4/3, respectively. Increasing the thickness of the STO barriers, hopping channels of higher order contribute more and more to the current transport as proven by measuring the T and V dependences. A crossover to variable range hopping behavior has been observed for junctions with thicker barriers (d ≥ 20 nm) in the high-V or high-T regime. By fitting the experimental data to theoretical models, physical parameters of the LS could be determined. For instance, the value of the localization length or radius of the localized state was determined to be ~ 4.6 × 10^− 8 cm which corresponds to the lattice constant of the STO unit cell. A value of ~ 6 × 10¹⁹ (eV)^− 1 cm^− 3 was calculated for the density of LS and the average barrier height was estimated as ~ 0.4 eV.     

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.     

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.     

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.     

New dielectric material system of x(Mg0.95Zn0.05Ti)O3-(1 − x)Ca0.8Sm0.4/3TiO3 at microwave frequency

The microstructures and the microwave dielectric properties of the x(Mg_0.95Zn_0.05)TiO₃-(1 − x) Ca_0.8Sm_0.4/3TiO₃ ceramic system were investigated. In order to achieve a temperature-stable material, we studied a method of combining a positive temperature coefficient material with a negative one. Ca_0.8Sm_0.4/3TiO₃ has dielectric properties of dielectric constant ε_r ~ 120, Q × f value ~ 13,800 GHz and a large positive τ_f value ~ 400 ppm/°C. (Mg_0.95Zn_0.05)TiO₃ possesses high dielectric constant (ε_r ~ 16.21), high quality factor (Q × f value ~ 210,000 at 9 GHz) and negative τ_f value (− 59 ppm/°C). Sintering at 1300 °C with x = 0.9, 0.9(Mg_0.95Zn_0.05Ti)O₃ − 0.1 Ca_0.8Sm_0.4/3TiO₃ has a dielectric constant (ε_r) of 22.7, a Q × f value of 124,000 GHz and a temperature coefficient of resonant frequency (τ_f) of − 6.3 ppm/°C.     

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.     

Structural and ferroelectric properties of La modified Sr0.8Bi2.2Ta2O9 thin films

La modified SBT (Sr_0.8La_0.1Bi_2.1Ta₂O₉) thin films of different thickness were fabricated on Pt/Ti/SiO₂/Si substrates by the metalorganic decomposition technique. All the films were annealed layer-by-layer at 800 °C using a rapid thermal annealing furnace. X-ray diffraction analysis indicated that the relative intensity of the (2 0 0) diffraction peak [I(2 0 0)/I(1 1 5)] increased with the increase of the film thickness. Eventually, an a-axis preferentially oriented SLBT film was obtained. These results are discussed with respect to the anisotropy of the grain growth. The a-axis preferentially oriented SLBT film, whose relative intensity of the (2 0 0) peak [I(2 0 0)/I(1 1 5)] was 1.05, had a remanent polarization (2P_r) value of 21 μC/cm² and a coercive field (2E_c) value of 70 kV/cm under the electric field of 200 kV/cm.     

Magnetic coupling in La0.67Ca0.33MnO3/La0.67Sr0.33CoO3/La0.67Ca0.33MnO3 sandwiches

La_0.67Ca_0.33MnO₃ (LCMO)/La_0.67Sr_0.33CoO₃ (LSCO)/LCMO trilayer films are fabricated on single-crystal substrates NdGaO₃ (110) and the interlayer coupling are investigated. Compared with LCMO single layer, sandwiches showed the enhanced metal-insulator transition temperature of LCMO layers. The magnetoresistance is dependent on spacer thickness and the peak value dramatically decreases when LSCO layer is thick enough because of shorting by the LSCO layer. The magnetic coercivity H_C shows a nonmonotonic behavior with changing spacer layer thickness and the waist-like hysteresis indicates that there is an indirect exchange coupling between the top and bottom LCMO layers across the spacer layer.     

Anisotropic and excellent magnetocaloric properties of La0.7Ca0.3MnO3 single crystal with anomalous magnetization

Magnetic properties and the magnetocaloric effect (MCE) have been investigated in La_0.7Ca_0.3MnO₃ single crystal with applied field along both the ab-plane and the c-direction. Due to the magnetocrystalline anisotropy, the crystal exhibits anisotropy in the MCE. Upon application of a 5 T field, the magnetic entropy changes (ΔS_M), reaching values of 7.668 J/(kg K) and 6.412 J/(kg K) for both the ab-plane and the c-direction, respectively. A magnetic entropy change of 3.3 J/(kg K) was achieved for a magnetic field change of 1.5 T at the Curie temperature, T_C = 245 K. Due to the absence of grains in the single crystal, the ΔS_M distribution here is much more uniform than for gadolinium (Gd) and other polycrystalline manganites, which is desirable for an Ericsson-cycle magnetic refrigerator. For a field change of 5 T, the relative cooling power, RCP, reached 358.17 J/kg, while the maximum adiabatic temperature change of 5.33 K and a magnetoresistance (MR) ratio of 507.88% at T_C were observed. We analysed the magnetization of La_0.7Ca_0.3MnO₃ single crystal at T_C and estimated several parameters of spin fluctuation on the basis of a self-consistent renormalization theory of spin fluctuations, with reciprocal susceptibility above T_C. We found that the magnetic property of La_0.7Ca_0.3MnO₃ is weakly itinerant ferromagnetic. A large reversible MCE and no hysteresis loss with a considerable value of refrigerant capacity indicate that La_0.7Ca_0.3MnO₃ single crystal is a potential candidate as a magnetic refrigerant.     

Synthesis of La0.5A0.5MnO3 (A = Sr, Ba) by a hydrothermal method at low temperature

A mild hydrothermal method has been adopted to prepare La_0.5Sr_0.5MnO₃ and La_0.5Ba_0.5MnO₃, which is of interest for a number of possible applications. The results from X-ray diffraction (XRD) indicate that in the present work the temperature of 200 and 240 °C are sufficient to prepare phase pure La_0.5Sr_0.5MnO₃ and La_0.5Ba_0.5MnO₃ crystals. At 200 °C, La_0.5Sr_0.5MnO₃ nanowires are obtained. The average width and length of the nanowires are 40 nm and 4 μm, respectively. At 240 °C, La_0.5Ba_0.5MnO₃ powders obtained have a cubic structure with the average size of 3-5 μm.     

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.     

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.     

Fluorescent tags to visualize defects in Al2O3 thin films grown using atomic layer deposition

Defects and cracks in thin film barriers that are coated on polymers allow the leakage of reactive species through the polymer substrate. Fluorescent tags have been developed to visualize defects and cracks in thin film barriers and to inspect rapidly the barrier quality with minimal sample preparation. For Al₂O₃ films with a thickness of 25 nm deposited on polyethylene naphthalate polymer substrates using atomic layer deposition techniques, the fluorescent tags have identified cracks ~ 20 nm in width after applied strain and have observed individual defects as small as ~ 200 nm in diameter.     

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.     

Self-patterned Nano Structures in Structurally Gradient Epitaxial La0.5Ba0.5CoO3 Films

Highly epitaxial La_0.5Ba_0.5CoO₃ (LBCO) thin films with sharp interface and a thickness of 200 nm were epitaxially grown on (001) SrTiO₃ substrates using pulsed laser deposition. High-resolution transmission electron microscopy and electron diffraction analysis revealed that the films have a triple-layered structure. The first layer, close to the film/substrate interface, has a thickness of ~ 6 nm and is a defect free single crystal disordered cubic structure (a = 3.882 Å) which has a lattice mismatch of − 0.59% with respect to the substrate. The second layer which dominates the film structure has a single crystal disordered cubic structure (a = 3.854 Å) which has a lattice mismatch of − 1.31% with respect to the substrate. The third layer located on the top of the film has a thickness of several nanometers and consists of 112-type ordered tetragonal structure. The cubic structures in the first and second layer have an orientation relationship of (001)_LBCO//(001)_STO and < 100 > _LBCO//< 100 > _STO with respect to the substrate. Self-patterned 3-dimensional nano structures with a dimension range from 2 to 10 nm were formed in the second and third layers. These nano structures were formed by the enclosure of anti-phase boundary planes which are parallel to the {100} of the cubic structure. Epitaxial LBCO thin films with such nano structures are hard ferromagnetic with a large coercive field value and magnetoresistance effect value (~ 24%), and exhibit semiconductor behavior at temperatures < 300 K.     

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.