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.     

Diluting and annealing effects on electromigration and morphology of chemical vapor-deposited copper films

The crystallization and orientation of chemical vapor-deposited copper films were investigated by means of X-ray diffraction. The ratios of Cu (1 1 1) peak intensity to Cu (2 0 0) [I(1 1 1)/I(2 0 0)] of the film deposited at different temperatures were plotted as a function of temperature. Then it can be found that the ratio of I(1 1 1)/I(2 0 0) increased with the deposition temperature, and 400 °C is the best one for electromigration when the films are grown in diluting N₂, and/or annealing by N₂ or by H₂. In addition, the morphology of copper films was characterized by atomic force microscopy, and it was found that the smoothness of the films grown in diluting N₂ and/or annealing by N₂ are improved, while the films annealing by H₂ have no significant changes.     

Variations of microstructures and electrical properties of Bi4Ti3O12/SrTiO3/(La0.5, Sr0.5)CoO3/MgO epitaxial thin films by annealing

Epitaxial thin films of a heterostructure with Bi₄Ti₃O₁₂(BIT)/SrTiO₃(ST) were successfully grown with a bottom electrode consisting of La_0.5Sr_0.5CoO₃(LSCO) on MgO(001) substrates using pulsed laser deposition. The grown BIT and ST (001) planes were parallel to the growth surface with the orientation relationship of BIT <110>//ST <010>. In the as-deposited film, the BIT (001) plane appeared to expand to relieve a lattice mismatch with the ST (001) plane. However, annealing for 20-40 min induced the BIT (001) plane to contract horizontally with its c-axis expanding, which was associated with a local perturbation in the layer stacking of the BIT structure. This structural distortion was reduced in the film annealed for 1 h, with restoration of the periodicity of the layer stacking. Correspondingly, the dielectric constant of the as-deposited film was increased from 292 to 411 by annealing for 1 h. In parallel, the film was paraelectric but became more ferroelectric, with the remanent polarization and the coercive field changing from 0.1 μC/cm² and 14 kV/cm to 1.7 μC/cm² and 69 kV/cm, respectively.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Effects of Mg doping on structural, optical, and electrical properties of CuScO2(0001) epitaxial films

CuScO₂ thin films with different Mg concentrations were grown on a-plane sapphire substrates by combining the two-step deposition and post-annealing techniques using Cu₂(Sc_1−xMg_x)₂O_y [X = 0.01, 0.05, 0.10] targets. The effects of the Mg doping in the Sc-site on the structural, optical, and electrical properties of the films were investigated. A Mg-doped CuScO₂[3R](0001) epitaxial film was obtained at a Mg concentration of 1 at%. The slight increase in the a-axis lattice constant and the slight decrease in the c-axis lattice constant of the film were confirmed using two-dimensional X-ray reciprocal space mapping. No significant increase in optical absorption was observed in the film, and the energy gap for direct allowed transition was estimated at 3.7 eV. The film showed an increase in the electrical conductivity and carrier concentration and a decrease in the Hall mobility compared with those of the non-doped epitaxial film. The decrease in the overlap of Cu 3d orbitals due to the increase in the a-axis lattice constant is one cause of the decrease in the Hall mobility of the film. The temperature dependence of the electrical transport properties of the film exhibited semiconducting characteristics, and the activation energy estimated from the temperature dependence of the carrier concentration was 0.55 eV.     

Properties of La-substituted Na0.5Bi4.5Ti4O15 ferroelectric thin films

Ferroelectric Na_0.5La_0.5Bi₄Ti₄O₁₅ (NaLaBTi) thin films were prepared by a chemical solution deposition method. The NaLaBTi thin films annealed at 750 °C under oxygen atmosphere were randomly oriented polycrystalline. Electrical properties of the NaLaBTi thin films were compared to Na_0.5Bi_4.5Ti₄O₁₅ thin films and better properties were observed in the NaLaBTi thin films. Remnant polarization (2P_r) and coercive electric field (2E_c) were 43 µC/cm² and 204 kV/cm at an applied electric field of 478 kV/cm, respectively. Leakage current density was 1.95 × 10^− 6 A/cm² at 100 kV/cm. Dielectric constant and dielectric loss were 805 and 0.05 at 1 kHz, respectively. Switchable polarization was suppressed by 15% after 1.44 × 10¹⁰ switching cycles.     

Synthesis, crystal structure and infrared study of LiEr(PO3)4

A single-crystal X-ray diffraction analysis has been performed on LiEr(PO₃)₄ prepared by the flux method. The compound crystallizes in the monoclinic system with space group C2/c and cell parameters: a = 16.262(2), b = 7.032(1), c = 9.549(2) Å and β = 125.95(1)°. The crystal structure was refined based on 1272 independent reflections with I > 2σ(I). Final values of the reliability factors were improven considerably: R(F²) = 0.0180 and wR(F²) = 0.0490. The LiEr(PO₃)₄ structure is characterized by infinite chains (PO₃)_n, extending parallel to the b direction. The ErO₈ dodecahedra and LiO₄ tetrahedra alternate on two-fold axes in the middle of four (PO₃)_n chains. The vibrational study by infrared absorption spectroscopy is reported.     

Structural characterization, thermal, spectroscopic and magnetic studies of the (C3H12N2)0.75[Mn1.50Fe1.50(AsO4)F6] and (C3H12N2)0.75[Co1.50Fe1.50(AsO4)F6] compounds

The (C₃H₁₂N₂)_0.94[Mn_1.50Fe_1.50^III(AsO₄)F₆] and (C₃H₁₂N₂)_0.75[Co_1.50Fe_1.50^III(AsO₄)F₆] compounds 1 and 2 have been synthesized using mild hydrothermal conditions. These phases are isostructural with (C₃H₁₂N₂)_0.75[Fe_1.5^IIFe_1.5^III(AsO₄)F₆]. The compounds crystallize in the orthorhombic Imam space group. The unit cell parameters calculated by using the patterns matching routine of the FULPROOF program, starting from the cell parameters of the iron(II),(III) phase, are: a = 7.727(1) Å, b = 11.047(1) Å, c = 13.412(1) Å for 1 and a = 7.560(1) Å, b = 11.012(1) Å, c = 13.206(1) Å for 2, being Z = 8 in both compounds. The crystal structure consists of a three-dimensional framework constructed from edge-sharing [M^II(1)₂O₂F₈] (M = Mn, Co) dimeric octahedra linked to [Fe^III(2)O₂F₄] octahedra through the F(1) anions and to the [AsO₄] tetrahedra by the O(1) vertex. This network gives rise two kinds of chains, which are extended in perpendicular directions. Chain 1 is extended along the a-axis and chain 2 runs along the c-axis. These chains are linked by the F(1) and O(1) atoms and establish cavities delimited by eight or six polyhedra along the [1 0 0] and [0 0 1] directions, respectively. The propanediammonium cations are located inside these cavities. The thermal study indicates that the structures collapse with the calcination of the organic dication at 255 and 285 °C for 1 and 2, respectively. The Mössbauer spectra in the paramagnetic state indicate the existence of two crystallographically independent positions for the iron(III) cations and a small proportion of this cation in the positions of the divalent Mn(II) and Co(II) ones. The IR spectrum shows the protonated bands of the H₂N- groups of the propanediamine molecule and the characteristic bands of the [AsO₄]³⁻ arsenate oxoanions. In the diffuse reflectance spectra, it can be observed the bands characteristic of trivalent iron(III) cation and divalent Mn(II) and Co(II) ones in a distorted octahedral symmetry. The calculated Dq and B-Racah parameters for the cobalt(II) phase are 710 and 925 cm⁻¹, respectively. The ESR spectra of compound 1 maintain isotropic with variation in temperature, being g = 1.99. Magnetic measurements for both compounds indicate that the main magnetic interactions are antiferromagnetic in nature. However, at low temperatures small ferromagnetic components are detected, which are probably due to a spin decompensation of the two different metallic cations. The hysteresis loops give values of the remnant magnetization and coercive field of 84.5, 255 emu/mol and 0.01, 0.225 T for phases 1 and 2, respectively.     

Nd-substituted SrBi2Ta2O9 ferroelectric thin films prepared by radio frequency magnetron sputtering

Nd-substituted SrBi₂Ta₂O₉ (SNBT) thin films are sputtered on Pt/Ta/SiO₂/Si substrates. X-ray diffraction and x-ray photoelectron spectroscopy studies indicate that Nd³⁺ is substituted into the bismuth layered perovskite structure, preferentially at the Sr²⁺ site. The annealed thin film is polycrystalline with plate/needle-like grain microstructure. Secondary ion mass spectrometry results show that elements in SNBT thin film homogeneously distribute along film depth and interfacial diffusion takes place during post annealing. The Nd substitution leads to enhanced remnant polarization (2P_r = 18 μC/cm²) and reduced coercivity (2E_c = 64 kV/cm) at 180 kV/cm measured at 25 °C. After 10¹⁰ switching cycles, around 9% remnant polarization is decreased.     

Synthesis and characterization of Nb2AlC thin films

We report on the synthesis and characterization of epitaxial c-axis oriented Nb₂AlC thin films deposited on c-axis sapphire (Al₂O₃) substrates by magnetron sputtering. Selected area electron diffraction reveal that independent of substrate temperature or film stoichiometry, there is the growth of a secondary phase not found in bulk, Nb₅Al₃C_x with a- and c-axis lattice constants of 7.746 Å and 5.246 Å, respectively. Scanning electron micrographs reveal large surface features, many with hexagonal shape and faceted texture. Atomic force microscopy topographical measurements indicate a surface roughness of approximately 15% of the total film thickness. Electrical transport measurements show typical metal-like conduction with a room temperature resistivity of ≈ 0.9 μΩ-m and a residual resistivity ratio of 2.5. A superconducting transition was found at ≈ 440 mK.     

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.     

Effect of processing on the properties of Bi3.15Nd0.85Ti3O12 thin films

Various crystallization parameters were studied during the fabrication of Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT) thin films on Pt/Ti/SiO₂/Si (100) by metal organic solution decomposition method. The effect of crystallization processes, crystallization ambients on the properties of BNdT thin films such as orientation, ferroelectric properties were examined. By adopting different fabrication processes, it is possible to get both highly c-axis oriented as well as randomly oriented thin films. Highly c-axis oriented BNdT thin film showed a large remnant polarization (2P_r) of 70 μC/cm² at an applied voltage of 10 V and exhibited a fatigue free behavior unto 2 × 10⁹ switching cycles. The improved ferroelectric properties of BNdT thin films suggest their suitability for high density ferroelectric random access memory applications.     

New compounds Cu2MnTi3S8 and Cu2NiTi3S8 with thiospinel structure

Cu₂MnTi₃S₈ and Cu₂NiTi₃S₈ compounds were prepared by high-temperature synthesis. The crystal structure of these quaternary phases was investigated by X-ray powder diffraction. The compounds are described in the thiospinel structure (space group ) with the lattice constants a = 1.00353(1) nm (Cu₂MnTi₃S₈) and a = 0.99716(1) nm (Cu₂NiTi₃S₈). The atomic parameters were calculated in anisotropic approximation (R_I = 0.0456 and R_I = 0.0520 for Cu₂MnTi₃S₈ and Cu₂NiTi₃S₈, respectively).     

Multiferroic properties of BiFeO3/Bi4Ti3O12 double-layered thin films fabricated by chemical solution deposition

Multiferroic BiFeO₃/Bi₄Ti₃O₁₂ (BFO/BTO) double-layered film was fabricated on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The effect of an interfacial BTO layer on electrical and magnetic properties of BFO was investigated by comparing those of pure BFO and BTO films prepared by the same condition. The X-ray diffraction result showed that no additional phase was formed in the double-layered film, except BFO and BTO phases. The remnant polarization (2P_r) of the double-layered film capacitor was 100 μC/cm² at 250 kV/cm, which is much larger than that of the pure BFO film capacitor. The magnetization-magnetic field hysteresis loop revealed weak ferromagnetic response with remnant magnetization (2M_r) of 0.4 kA/m. The values of dielectric constant and dielectric loss of the double-layered film capacitor were 240 and 0.03 at 100 kHz, respectively. Leakage current density measured from the double-layered film capacitor was 6.1 × 10^− 7 A/cm² at 50 kV/cm, which is lower than the pure BFO and BTO film capacitors.     

[NH3(CH2)2NH3][Co(SO4)2(H2O)4]: Chemical preparation, crystal structure, thermal decomposition and magnetic properties

Cobalt ethylenediammonium bis(sulfate) tetrahydrate, [NH₃(CH₂)₂NH₃][Co(SO₄)₂(H₂O)₄], has been synthesised by slow evaporation at room temperature. It crystallises in the triclinic system, space group , with the unit cell parameters: a = 6.8033(2), b = 7.0705(2), c = 7.2192(3) Å, α = 74.909(2)°, β = 72.291(2)°, γ = 79.167(2)°, Z = 1 and V = 317.16(2) Å³. The Co(II) atom is octahedrally coordinated by four water molecules and two sulfate tetrahedra leading to trimeric units [Co(SO₄)₂(H₂O)₄]. These units are linked to each other and to the ethylenediammonium cations through OW-H…O and N-H…O hydrogen bonds, respectively. The zero-dimensional structure is described as an alternation between cationic and anionic layers along the crystallographic b-axis. The dehydration of the precursor proceeds through three stages leading to crystalline intermediary hydrate phases and an anhydrous compound. The magnetic measurements show that the title compound is predominantly paramagnetic with weak antiferromagnetic interactions.     

Synthesis, structure refinement at 296 K and physico-chemical characterizations of KMnHP3O10

Potassium manganese(III) monohydrogentriphosphate KMnHP₃O₁₀ was synthesized by flux method and characterized by single-crystal X-ray diffraction, crystallizes in the monoclinic system with centric space group C2/c. The parameters of the unit cell are a = 12.104(1), b = 8.287(1). c = 9.150(1) Å, β = 110.97(1)° and Z = 4. The structure was solved at 296 K using 893 independent reflections and refined until R(F) = 0.022; wR(F²) = 0.045. The atomic arrangement of the title compound consists of MnO₆ octahedra linked by hydrogentriphosphate anions to form a three-dimensional framework containing tunnels parallel to the c-axis where the K⁺ cations are inserted. The structure of KMnHP₃O₁₀ contains a single Mn site which is surrounded by typical Jahn-Teller [2 + 2 + 2] distorted octahedron. The title material has been also characterized by different physico-chemical techniques: powder X-ray diffraction, IR, NMR and CI spectroscopies and DTA-TGA-DSC thermal analysis.     

V-doping effects on ferroelectric properties of K0.5Bi4.5Ti4O15 thin films

V-doped K_0.5Bi_4.5Ti₄O₁₅ (K_0.5Bi_{4.5 − x/3}Ti_4 − xV_xO₁₅, KBTiV-x, x = 0.00, 0.01, 0.03, and 0.05) thin films were prepared on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. The thin films were annealed by using a rapid thermal annealing process at 750 °C for 3 min in an oxygen atmosphere. Among them, KBTiV-0.03 thin film exhibited the most outstanding electrical properties. The value of remnant polarization (2P_r) was 75 μC/cm² at an applied electric field of 366 kV/cm. The leakage current density of the thin film capacitor was 5.01 × 10⁻⁸ at 100 kV/cm, which is approximately one order of magnitude lower than that of pure K_0.5Bi_4.5Ti₄O₁₅ thin film capacitor. We found that V doping is an effective method for improving the ferroelectric properties of K_0.5Bi_4.5Ti₄O₁₅ thin film.     

Synthesis, structure and magnetic properties of a new iron phosphonate-oxalate with 3D framework: [Fe(O3PCH3)(C2O4)0.5(H2O)]

A new iron phosphonate-oxalate [Fe(O₃PCH₃)(C₂O₄)_0.5(H₂O)] (1), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction studies reveal that 1 consists of layers of vertex-linked FeO₆ octahedra and O₃PC tetrahedra, which are further connected by bis-chelate oxalate bridges, giving to a 3D structure with 10-membered channels. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.851(2) Å, b = 16.803(7) Å, c = 7.941(4) Å, β = 107.516(6)°, V = 617.2(5) Å³, Z = 4, R₁ = 0.0337 and wR₂=0.0874 for 1251 reflections [I > 2σ(I)]. Mössbauer spectroscopy measurement confirms the existence of high-spin Fe(III) in 1. Magnetic studies show that 1 exhibits weak ferromagnetism with T_N = 30 K due to a weak spin canting.     

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.     

Tl2Ba2CaCu2O8 thin films on 2 in. LaAlO3(0 0 1) substrates

High quality Tl₂Ba₂CaCu₂O₈ (Tl-2212) superconducting thin films are prepared on both sides of 2 in. LaAlO₃(0 0 1) substrates by off-axis magnetron sputtering and post-annealing process. XRD measurements show that these films possess pure Tl-2212 phase with C-axis perpendicular to the substrate surface. The thickness unhomogeneity of the whole film on the 2 in. wafer is less than 5%. The superconducting transition temperatures T_cs of the films are around 105 K. At zero applied magnetic field, the critical current densities J_cs of the films on both sides of the wafer were measured to be above 2 × 10⁶ A/cm² at 77 K. The microwave surface resistance R_s of film was as low as 350 μΩ at 10 GHz and 77 K. In order to test the suitability of Tl-2212 thin films for passive microwave devices, 3-pole bandpass filters have been fabricated from double-sided Tl-2212 films on LaAlO₃ substrates.