Epitaxial thin films of (Bi0.9La0.1)2NiMnO6 obtained by pulsed laser deposition

Bulk Bi₂NiMnO₆ has been shown to be ferromagnetic and ferroelectric. Here, we report a systematic study of the influence of the deposition conditions on the growth of (Bi_0.9La_0.1)₂NiMnO₆ thin films onto (0 0 1) SrTiO₃ substrates by pulsed laser deposition. Oxygen pressure and substrate temperature have been varied from 0.3 to 0.6 mbar and 600 to 660 °C, respectively. Whereas it is found that single-phase and epitaxial films can be obtained in a relatively broad oxygen pressure range, the temperature window, centred on 620 °C, is extremely narrow. Films of low roughness, about 1 unit cell, have been obtained. It is found that the magnetisation of the films, which are ferromagnetic with Curie temperatures about 100 K, is lower than the expected theoretical value, which might be attributed to an incomplete Ni-O-Mn long-range ordering.     

Formation of highly textured (1 1 1) Bi2O3 films by anodization of electrodeposited bismuth films

Highly textured bismuth oxide (Bi₂O₃) thin films have been prepared using anodic oxidation of electrodeposited bismuth films onto stainless steel substrates. The Bi₂O₃ films were uniform and adherent to substrate. The Bi₂O₃ films were characterized for their structural and electrical properties by means of X-ray diffraction (XRD), electrical resistivity and dielectric measurement techniques. The X-ray diffraction pattern showed that Bi₂O₃ films are highly textured along (1 1 1) plane. The room temperature electrical resistivity of the Bi₂O₃ films was 10⁵ Ω cm. Dielectric measurement revealed normal oxide behavior with frequency.     

The influence of oxidation temperature on structural, optical and electrical properties of thermally oxidized bismuth oxide films

Monoclinic bismuth oxide (Bi₂O₃) films have been prepared by thermal oxidation of vacuum evaporated bismuth thin films onto the glass substrates. In order to obtain the single phase Bi₂O₃, the oxidation temperature was varied in the range of 423-573 K by an interval of 50 K. The as-deposited bismuth and oxidized Bi₂O₃ films were characterized for their structural, surface morphological, optical and electrical properties by means of X-ray diffraction, scanning electron microscopy (SEM), optical absorption and electrical resistivity measurements, respectively. The X-ray analyses revealed the formation of polycrystalline mixed phases of Bi₂O₃ (monoclinic, α-Bi₂O₃ and tetragonal, β-Bi₂O₃) at oxidation temperatures up to 523 K, while at an oxidation temperature of 573 K, a single-phase monoclinic α-Bi₂O₃ was formed. From SEM images, it was observed that of as-deposited Bi films consisted of the well-defined isolated crystals of different shapes while after thermal oxidation the smaller dispersed grains were found to be merged to form bigger grains. The changes in the optical properties of Bi₂O₃ films obtained by thermal oxidation at various temperatures were studied from optical absorption spectra. The electrical resistivity measurement depicted semiconducting nature of Bi₂O₃ with high electrical resistivity at room temperature.     

Room-temperature multiferroic properties of Bi4.15Nd0.85Ti3FeO15 thin films prepared by the metal–organic decomposition method

Aurivillius-structured Bi_4.15Nd_0.85Ti₃FeO₁₅ multiferroic thin films with four perovskite slabs were deposited on Pt/Ti/ SiO₂/Si substrates by the metal–organic decomposition method. The structural, dielectric and multiferroic properties of the films were investigated. Good ferroelectric behavior along with large dielectric constant and small loss factor were observed at room temperature. A weak ferromagnetic rather than an antiferromagnetic property was observed at room temperature by magnetic measurement. Moreover, the ferromagnetic property was enhanced when the temperature was below 13 K and a large saturation magnetization of about 5.4 emu/cm³ was obtained at 4 K. Possible reasons are put forward to discuss the complicated magnetic property.     

Piezoresponse force microscopy and magnetic force microscopy characterization of γ-Fe2O3-BiFeO3 nanocomposite/Bi3.25La0.75Ti3O12 multiferroic bilayers

The multiferroic behavior of epitaxial γ-Fe₂O₃-BiFeO₃ (composite)/Bi_3.25La_0.75Ti₃O₁₂ bi-layered heterostructures grown on SrRuO₃/SrTiO₃ (1 1 1) substrates has been studied using piezoresponse force microscopy, magnetic force microscopy and magnetometry. The ferroelectric domain structure is ascribed to the BiFeO₃ phase while the magnetism originates in the γ-Fe₂O₃ phase of the composite layer. Our studies demonstrate the presence and switching of magnetic and ferroelectric domains within the same area of the sample. This confirms the presence of multiferroic behavior at the nanoscale in our γ-Fe₂O₃-BiFeO₃ nanocomposite thin films.     

Improved multiferroic properties and a novel magnetic behavior of Bi0.8La0.2Fe1−xCoxO3 nanoparticles

Bi_0.8La_0.2Fe_1−xCo_xO₃ nanoparticles of single phase (BLFCO_x, x=0, 0.005, 0.01, 0.02) were prepared by a sol-gel method using polyvinyl alcohol as a surfactant. Co substitution at Fe site improved further dielectric properties of Bi_0.8La_0.2FeO₃ nanoparticles in the frequency range below 25 MHz at room temperature. Magnetization at 10 kOe, coercivities, and remanence of BLFCO_x nanoparticles increased with increasing Co content. It is interesting that the hysteresis loop of all the BLFCO_x nanoparticles presented a wasp-waisted shape. The property can open an important way to design new multiferroic applications of low hysteresis loss in low magnetic fields.     

Influence of substrate temperature on structures and dielectric properties of pyrochlore Bi1.5Zn1.0Nb1.5O7 thin films prepared by pulsed laser deposition

The influence of substrate temperature on structural and dielectric properties of cubic pyrochlore Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films prepared by pulsed laser deposition process has been investigated. BZN thin films were deposited on Pt/Ti/SiO₂/Si(1 0 0) substrate and in situ annealed at 700 °C. The results indicate that the substrate temperature has a significant effect on the structural and dielectric properties of BZN thin films. The films exhibit a cubic pyrochlore structure in the substrate temperature range from 550 °C to 700 °C and at the annealing temperature of 700 °C. With further increase of substrate temperature to 750 °C, the phases of Bi₂O₃, BiNbO₄ and Bi₅Nb₃O₁₅ can be detected in the XRD pattern due to the Zn loss. The dielectric constant and loss tangent of the films deposited at 650 °C are 192 and 6 × 10⁻⁴ at 10 kHz, respectively. The tunability is 10% at a dc bias field of 0.9 MV/cm.     

Metastable structure and properties of (La0.73Bi0.27)0.67Ca0.33MnO3

The electrical transport and magnetic properties of high Bi doped (La_0.73Bi_0.27)_0.67Ca_0.33MnO₃ are studied at the temperature and magnetic field ranges from 10 to 300 K and 0 to 3 T. Significant temperature and magnetic field hystereses are observed in both resistivity and magnetization measurements. Meanwhile, an enhanced magnetoresistance effect, within a wide temperature window, is obtained in the (La_0.73Bi_0.27)_0.67Ca_0.33MnO₃. The hysteresis and enhanced magnetoresistance are discussed based on an inhomogeneous metastable structure related to the Bi dopant.     

Spray pyrolytic deposition of solid electrolyte Bi2V0.9Cu0.1O5.35 films

Copper substituted bismuth vanadate films have been successfully deposited first time by spray pyrolysis technique on glass substrates suitable for low temperature solid oxide fuel cells. Desired phase formation of polycrystalline Bi₂V_0.9Cu_0.1O_5.35 (BICUVOX.10) was confirmed by X-ray diffraction technique. These films were further studied with EDAX and SEM techniques for their compositional and morphological characterization. Electrical conductivity of BICUVOX.10 is found to be 5.7 × 10⁻² (Ω cm)⁻¹ at 698 K, predicts the onset temperature for ionic contribution suitable for low temperature SOFC applications. Room temperature complex impedance plot reveals that electrical process arises due to contribution from the grain interior.     

Effect of strontium substitution on the structural and magnetic properties of La1.8Sr0.2MMnO6 (M = Ni,Co)-layered manganites

Sr-substituted perovskites, La_1.8Sr_0.2MMnO₆ (M = Ni, Co), were synthesized using the solid-state reaction technique to present a systematic study on their morphological, structural and magnetic properties. The average grain size of the as-prepared La_1.8Sr_0.2NiMnO₆ samples are in the range of 0.2–0.7 µm and those for La_1.8Sr_0.2CoMnO₆ manganites are 0.1–2.8 μm, which is significantly less than that of unsubstituted La₂NiMnO₆ (LNMO) and La₂CoMnO₆ (LCMO) manganites. The XPS analysis enlightened about phase purity, binding energy and oxygen vacancy of La_1.8Sr_0.2MMnO₆ manganites. The Sr-substituted LNMO has revealed a sharp ferromagnetic to paramagnetic phase transition at 160 ± 2 K, which is about 120 K less than that of parent LNMO. The Sr-substituted LCMO exhibited such a transition at 220 ± 2 K, which is 8 K less than that of parent LCMO. The temperature-dependent magnetization measurements suggest that the effect of Sr on the transition temperature in LNMO is more significant than that of LCMO.     

Synthesis and characterization of apatite-type La9.67Si6-xAlxO26.5-x/2 electrolyte materials and compatible cathode materials

Apatite silicates have recently been reported as promising electrolyte materials for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this work, a series of apatite-type compounds La_9.67Si_6-xAl_xO_26.5-x/2 (LSAO) with x = 0-2 are synthesized by the sol-gel process at calcining temperature of 800-900 °C. Thermal expansion coefficient, relative density and electrical conductivity of these samples with different Al doped contents are investigated. A symmetrical cell, which is composed of La_9.67Si₅AlO₂₆ electrolyte and (La_0.74Bi_0.10Sr_0.16)MnO_3+δ (LBSM) cathode, is fabricated and electrochemically characterized. LBSM cathode shows a good electrochemical performance, which proves LBSM to be a promising candidate cathode for LSAO-based electrolyte.     

Structural, magnetic and magnetotransport behavior of La0.7SrxCa0.3−xMnO3 compounds

A systematic investigation of the structural, magnetic and electrical properties of a series of nanocrystalline La_0.7Sr_xCa_0.3−xMnO₃ materials, prepared by high energy ball milling method and then annealed at 900 °C has been undertaken. The analysis of the XRD data using the Win-metric software shows an increase in the unit cell volume with increasing Sr ion concentration. The La_0.7Sr_xCa_0.3−xMnO₃ compounds undergo a structural orthorhombic-to-monoclinic transition at x=0.15. Electric and magnetic measurements show that both the Curie temperature and the insulator-to-metal transition temperature increase from 259 K and 253 K correspondingly for La_0.7Ca_0.3MnO₃ (x=0) to 353 K and 282 K, respectively, for La_0.7Sr_0.3MnO₃ (x=0.3). It is argued that the larger radius of Sr²⁺ ion than that of Ca²⁺ is the reason to strengthen the double-exchange interaction and to give rise to the observed increase of transition temperatures. Using the phenomenological equation for conductivity under a percolation approach, which depends on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions, we fitted the resistivity versus temperature data measured in the range of 50-320 K and found that the activation barrier decreased with the raising Sr²⁺ ion concentration.     

Hydrothermal synthesis and Magnetocaloric effect of La0.5Ca0.3Sr0.2MnO3

The hydrothermal synthesis and magnetic entropy change for the perovskite manganite La_0.5Ca_0.3Sr_0.2MnO₃ have been studied. The La_0.5Ca_0.3Sr_0.2MnO₃ can be produced as phase-pure, crystalline powders in one step from solutions of metal salts in aqueous potassium hydroxide solution at a temperature of 513 K in 72 h. Scanning electron microscopy shows that the materials are made up of cuboid-shaped particles in typical dimension of 4.0×2.5×1.6 μm. Heat treatment can improve the magnetocaloric effect for the hydrothermal sample. The maximum magnetic entropy change ΔS_M for the as-prepared sample is 0.88 J kg⁻¹ K⁻¹ at 315 K for a magnetic field change of 2.0 T. It increases to 1.52 J kg⁻¹ K⁻¹, near its Curie temperature (317 K) by annealing the sample at 1473 K for 6 h. The hydrothermal synthesis method is a feasible route to prepare high-quality perovskite material for magnetic refrigeration application.     

Electrical properties of La2O3 thin films grown on TiN/Si substrates via atomic layer deposition

The electrical as well as the structural properties of La₂O₃ thin films on TiN substrates were investigated. Amorphous stoichiometric La₂O₃ thin films were grown at 300 °C via atomic layer deposition technique by using lanthanum 2,2,6,6-tetramethyl-3,5-heptanedione [La(TMHD)₃] and H₂O as precursors. Post-annealing of the grown film induced dramatic changes in structural and the electrical properties. Crystalline phases of the La₂O₃ film emerged with the increase of the post-annealing temperature. Metal-insulator-metal (MIM) capacitor was fabricated to measure the electrical properties of the grown film. The dielectric constant of the La₂O₃ thin films increased with annealing temperature to reach the value of 17.3 at 500 °C. The leakage current density of the film post-annealed at 400 °C was estimated to be 2.78 × 10⁻¹⁰ and 2.1 × 10⁻⁸ A/cm² at ±1 V, respectively.     

Magnetic resonances spectroscopy of nanosize particles La0.7Sr0.3MnO3

Using a co-precipitation method, perovskite-type manganese oxide La_0.7Sr_0.3MnO₃ nanoparticles (NPs) with particle size 12 nm were prepared. Detailed studies of both ⁵⁵Mn nuclear magnetic resonance and superparamagnetic resonance spectrum, completed by magnetic measurements, have been performed to obtain microscopic information on the local magnetic structure of the NP. Our results on nuclear dynamics provide direct evidence of formation of a magnetically dead layer, of the thickness ≈2 nm, at the particle surface. Temperature dependences of the magnetic resonance spectra have been measured to obtain information about complex magnetic properties of La_0.7Sr_0.3MnO₃ fine-particle ensembles. In particular, electron paramagnetic resonance spectrum at 300 K shows a relatively narrow sharp line, but as the temperature decreases to 5 K, the apparent resonance field decreases and the line width considerably increases. The low-temperature blocking of the NPs magnetic moments has been clearly observed in the electron paramagnetic resonances. The blocking temperature depends on the measuring frequency and for the ensemble of 12 nm NPs at 9.244 GHz has been evaluated as 110 K.     

Annealing effects on the structural and electrical transport properties of n-type Bi2Te2.7Se0.3 thin films deposited by flash evaporation

N-type Bi₂Te_2.7Se_0.3 thermoelectric thin films with thickness 800 nm have been deposited on glass substrates by flash evaporation method at 473 K. Annealing effects on the thermoelectric properties of Bi₂Te_2.7Se_0.3 thin films were examined in the temperature range 373-573 K. The structures, morphology and chemical composition of the thin films were characterized by X-ray diffraction, field emission scanning electron microscope and energy dispersive X-ray spectroscopy, respectively. Thermoelectric properties of the thin films have been evaluated by measurements of the electrical resistivity and Seebeck coefficient at 300 K. The Hall coefficients were measured at room temperature by the Van der Pauw method. The carrier concentration and mobility were calculated from the Hall coefficient. The films thickness of the annealed samples was measured by ellipsometer. When annealed at 473 K, the electrical resistivity and Seebeck coefficient are 2.7 mΩ cm and −180 μV/K, respectively. The maximum of thermoelectric power factor is enhanced to 12 μW/cm K².     

A high temperature powder neutron diffraction structural study of the apatite-type oxide ion conductor, La9.67Si6O26.5

High-resolution neutron powder diffraction studies of the oxide ion conductor La_9.67Si₆O_26.5 are reported for temperatures ranging between 25 and 900 °C. The best fit to the data was obtained for space group P6₃ and there was no evidence for any change in symmetry over the temperature range studied. Interstitial oxide ions are identified lying in sites similar to those predicted by previous computer modelling studies, and in agreement with structural studies on related materials. Furthermore, occupancy of these sites is enhanced by Frenkel-type disorder from neighbouring positions. The results thus add further weight to the interpretation that, in these apatite-type systems, the silicate substructure is important for the accommodation of interstitial oxide ions and their migration.     

Exchange bias in (1 1 0)-orientated Bi0.9La0.1FeO3/La0.5Ca0.5MnO3 films

We performed a systematic study on the exchange bias in (1 1 0)-orientated Bi_0.9La_0.1FeO₃/La_0.5Ca_0.5MnO₃ (BLFO/LCMO) heterostructure with a fixed BLFO film thickness of 600 nm and different LCMO layers ranging from t=0 to 30 nm. The LCMO is found to be weakly ferromagnetic, with the Curie temperature descending from ∼225 K to 0 as the layer thickness decreases from 30 nm to 3 nm. The main magnetic contributions come from the BLFO film, and the areal magnetization ratio is 1:0.07 for t=5 nm and 1:0.82 for t=30 nm for BLFO to LCMO at the temperature of 5 K. Further experiments show the presence of significant exchange bias, and it is, at the temperature of 10 K, ∼40 Oe for t=0 and ∼260 Oe for t=30 nm. The exchange bias reduces dramatically upon warming and disappears above the blocking temperature of the spin-glasslike behavior observed in the samples. The possible origin for exchange bias is discussed.     

Optical and electrical properties of thermally oxidized bismuth thin films

Bismuth trioxide (Bi₂O₃) thin films were prepared by dry thermal oxidation of metallic bismuth films deposited by vacuum evaporation. The oxidation process of Bi films consists of a heating from the room temperature to an oxidation temperature (T_o = 673 K), with a temperature rate of 8 K/min; an annealing for 1 h at oxidation temperature and, finally, a cooling to room temperature. The optical transmission and reflection spectra of the films were studied in spectral domains ranged between 300 nm and 1700 nm, for the transmission coefficient, and between 380 nm and 1050 nm for the reflection coefficient, respectively. The thin-film surface structures of the metal/oxide/metal type were used for the study of the static current-voltage (I-U) characteristics. The temperature of the substrate during bismuth deposition strongly influences both the optical and the electrical properties of the oxidized films. For lower values of intensity of electric field (ξ < 5 × 10⁴V/cm), I-U characteristics are ohmic.