Metallization of La1/3NbO3 by lithium incorporation

Lithium ion was successfully introduced into La_1/3NbO₃ with an A-site-deficient perovskite-type structure. The crystal structure and transport properties of La_1/3Li_xNbO₃ were investigated as a function of Li content (x = 0-0.59). The lattice parameters of La_1/3Li_xNbO₃ with an orthorhombic cell were enlarged with increasing Li content for x ≤ 0.3, and the structure was transformed to a pseudo-tetragonal cell for x = 0.44. The temperature dependence of electrical resistivity gradually changed from insulating to metallic with increasing x, and thermoelectric power measurement indicated that the carriers were electrons. In X-ray photoelectron spectra of the incorporated samples, Nb_3d⁴⁺ peaks appeared in addition to Nb_3d⁵⁺ peaks, which was consistent with the change of the transport properties. In spite of the success of metallization, no diamagnetic signal indicative of supercondcutivity was observed in La_1/3Li_0.59NbO₃ down to 1.8 K.     

Synthesis and crystal growing of La3NbO7

The conditions of synthesis of La₃NbO₇ by thermal treatment of coprecipitated lanthanum and niobium hydroxides have been investigated. The interaction was found to proceed to a considerable extent already at rather low temperatures, a well crystallized singlephase product being obtained at 900°C. Congruent melting of La₃NbO₇ was established at about 1800°C. The preparation of single crystals from melt in reducing and inert atmospheres leads to oxygen loss from La₃NbO₇ within the homogeneity range of Nb₂O₅. The oxygen deficiency could be eliminated by annealing the crystals in oxygen at 1500°C.     

Crystallographic and dielectric properties of the Pb2(MgW)O6-La1.33(MgW)O6 solid solutions

A continuous series of solid solutions was found to form with a perovskite structure in the given system. At room temperature the unit cells were cubic in the 1–65 mol% La_1.33(MgW)O₆ region and pseudotetragonally distorted in the 75–100 mol% La_1.33(MgW)O₆ region. In the latter region, an ordering of A-site vacancies was found to occur along alternate c-planes. The Curie temperature decreased rapidly with increasing La_1.33(MgW)O₆ content up to 10 mol%.     

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.     

Microwave dielectric properties of (Pb1−3x/2Lax)(Mg1/2W1/2)O3

La modified Pb(Mg_1/2W_1/2)O₃ were prepared by solid-state reaction process, and the sintering behavior, microstructure and microwave dielectric properties were investigated by X-ray powder diffraction (XRD), Raman scattering and HP network analyzer in this paper. A series of single phase perovskite type solid solutions with A-site vacancies (Pb_1−3x/2La_x(Mg_1/2W_1/2)O₃ (0 ≤ x ≤ 2/3)) were formed. The solid solution took cubic perovskite type structure (Fm3m) with random distribution of A-site vacancies when 0 < x < 0.5, and tetragonal or orthorhombic structure with the ordering of A-site vacancies when 0.5 ≤ x ≤ 2/3. The dielectric constant and temperature coefficient of resonant frequency decrease with increasing La content. Relatively good combination microwave dielectric properties were obtained for x = 0.56: ?_r = 28.7; Q × f = 18098; and τ_f = −5.8 ppm/°C.     

Superstructure determination of the perovskite βLa0.33NbO3

New interesting results in the crystal structure of the perovskite La_0.33NbO₃ were revealed using selected area electron diffraction, powder X-ray diffraction techniques and Rietveld refinement method. Although the superstructure of La_0.33NbO₃ could not be seen by conventional X-ray powder diffraction technique, the electron diffraction patterns revealed weak spots resulting in a superstructure array for the atoms of La_0.33NbO₃. The crystal symmetry is compatible with an orthorhombic cell, space group Cmmm. From Rietveld refinement, the resulting lattice parameters are: a = 7.82(1) Å, b = 7.83(9) Å, c = 7.90(9) Å and goodness of fit R = 0.1107, Rwp = 0.15. The superstructure is built from distorted octahedra NbO₆ along the [001] axis. Results suggest that this distortion may be produced by occupation of La atoms in (2a) and (4l) sites.     

Anomalous phase formation during annealing of La2O3 thin films deposited by ion beam assisted electron beam evaporation

The fifty seven nm thick La₂O₃ thin films were deposited on Si (100) substrates. After deposition, the amorphones thin films, were amorphous, were annealed at 750 and 900 °C for 1 h. It was found that their amorphous structure had been crystallized to hexagonal and cubic structures, respectively. The phase formation of the La₂O₃ thin films was anomalous at higher annealing temperatures. The theory of heterogeneous nucleation was used to interpret the anomalous phase formation of La₂O₃ films. To investigate the effects of the phase structure on these properties, Refractive indexes and dielectric constants of different structures of La₂O₃ films were measured.     

H2S sensing properties of La-doped nanocrystalline In2O3

The nanocrystalline powders of pure and La³⁺-doped In₂O₃ with cubic structure were prepared by a simple hydrothermal decomposition route. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). All the compositions exhibited a single phase, suggesting a formation of solid solution in the concentration of doping investigated. Gas-sensing properties of the sensor elements were tested by mixing a gas in air at static state, as a function of concentration of dopant, operating temperature and concentrations of the test gases. The pure In₂O₃ exhibited high response towards H₂S gas at an operating temperature 150 °C. Doping of In₂O₃ with La³⁺ increases its response towards H₂S and La³⁺ (5.0 wt.% La₂O₃)-doped In₂O₃ showed the maximum response at 125 °C. The selectivity of the sensor elements for H₂S against different reducing gases was studied. The results on response and recovery time were also discussed.     

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.     

Phase equilibrium and growth of homogeneous crystals in the γLa2S3  γNd2S3 system

T-x diagram of the γLa₂S₃  γNd₂S₃ system was plotted for the temperature interval 1400–2100°C. γLa₂S₃ and γNd₂S₃ form unlimited solid solutions of the substitution type. Basing on this phase diagram the theoretical distribution curves of Nd₂S₃ along the ingot of length were calculated. The experimental distribution curves were determined by chemical and electron microprobe measurements of La and Nd content in γ(La,Nd)₂S₃ ingots directionally solidified from the melt of different composition. Character of the component distribution in the ingots shows that diffusion of neodymium and lanthanum is exeptionally fast at 1700–2000°C. This phenomenon is explained by vacancy diffusion mechanism in γLa₂S₃  γNd₂S₃ solid solutions. Crystal structure of these solid solutions belongs to Th₃P₄ type with high concentration of randomly distributed cation vacancies.     

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.     

Stabilization of γ-La2S3 by alkali metal ion doping

La₃S₄ is known to crystallize in a defect cubic Th₃P₄ structure. The effect of alkali metal ion doping in the lacunar La_3−xS₄ structure has been studied. Compounds with molecular formula La_3−xA_xS₄ (A = Li, Na and K) with varying A/La ratios (0.1, 0.15, 0.2, 0.25 and 0.3) have been synthesized by gas-solid reaction method. The band gap increases with increase in dopant concentration. The optical properties show an increase in yellowness of the doped compositions when compared to the parent phase.     

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.     

Fabrication of transparent La2Hf2O7 ceramics from combustion synthesized powders

Transparent La₂Hf₂O₇ (LHO) ceramics were, for the first time, successfully fabricated from combustion-synthesized powders. Nanosized La₂Hf₂O₇ powders were obtained through combustion reaction, using glycine or EDTA as a fuel. The as-made powders were isostatically pressed at 180 MPa and then sintered at 1850 °C for 6 h in hydrogen atmosphere. The resulting ceramics have high optical transmittance.     

Influence of sintering temperature on piezoelectric properties of (K0.5Na0.5)NbO3-LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ have been synthesized by traditional ceramics process without cold-isostatic pressing. The effect of the content of LiNbO₃ and the sintering temperature on the phase structure, the microstructure and piezoelectric properties of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics were investigated. The result shows that the phase structure transforms from the orthorhombic phase to tetragonal phase with the increase of the content of LiNbO₃, and the orthorhombic and tetragonal phase co-exist in (K_0.5Na_0.5)NbO₃-LiNbO₃ ceramics when the content of LiNbO₃ is about 0.06 mol. The sintering temperature of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ decreases with the increase of the content of LiNbO₃. The optimum composition for (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics is 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃. The optimum sintering temperature of 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics is 1080 °C. Piezoelectric properties of 0.94 (K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics under the optimum sintering temperature are piezoelectric constant d₃₃ of 215 pC/N, planar electromechanical coupling factor k_p of 0.41, thickness electromechanical coupling factor k_t of 0.48, the mechanical quality factor Q_m of 80, the dielectric constant of 530 and the Curie temperature T_c = 450 °C, respectively. The results indicate that 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ piezoelectric ceramics is a promising candidate for lead-free piezoelectric ceramics.     

Microwave dielectric properties of Ba2 − xSrxLa3Ti3NbO15 ceramics

High dielectric constant and low loss ceramics in the system Ba_2 − xSr_xLa₃Ti₃NbO₁₅ (x = 0-1) have been prepared by conventional solid-state ceramic route. Ba_2 − xSr_xLa₃Ti₃NbO₁₅ solid solutions adopted A₅B₄O₁₅ cation-deficient hexagonal perovskite structure for all compositions. The materials were characterized at microwave frequencies. They show a linear variation of dielectric properties with the value of x. Their dielectric constant varies from 48.34 to 43.03, quality factor Q_u × f from 20,291 to 39,088 GHz and temperature variation of resonant frequency from 8 to 1.39 ppm/°C as the value of x increases. These low loss ceramics might be used for dielectric resonator (DR) applications.     

Synthesis, crystal structure and thermal decomposition of [La2(CH3CH2COO)6·(H2O)3]·3.5H2O precursor for high-k La2O3 thin films deposition

Lanthanum acetylacetonate La(C₅H₇O₂)₃·xH₂O has been used in the preparation of the precursor solution for the deposition of polycrystalline La₂O₃ thin films on Si(1 1 1) single crystalline substrates. The precursor chemistry of the as-prepared coating solution, precursor powder and precursor single crystal have been investigated by Fourier Transformed Infrared Spectroscopy (FTIR), differential thermal analysis coupled with quadrupole mass spectrometry (TG-DTA-QMS) and X-ray diffraction. The FTIR and X-ray diffraction analyses have revealed the complex nature of the coating solution due to the formation of a lanthanum propionate complex. The La₂O₃ thin films deposited by spin coating on Si(1 1 1) substrate exhibit good morphological and structural properties. The films heat treated at 800 °C crystallize in a hexagonal phase with the lattice parameters a = 3,89 Å and c = 6.33 Å, while at 900 °C the films contain both the hexagonal and cubic La₂O₃ phase.     

Europium niobium bronzes

The structural and the electrical properties of the europium niobium bronzes with various europium and oxygen compositions (Eu_xNbO_y) have been investigated. A niobium bronze with a stoichiometric oxygen content, namely y = 3, is tetragonal for x = 0.5 ? 0.65 and cubic for x = 0.65 ? 1.00. A niobium bronze with full oxygen vacancies, Eu_xNbO_2+x, where all europium and niobium ions are in bivalent and tetravalent states respectively, crystallizes in the cubic form in the single-phase region (0.5 < x < 1.0). The cubic niobium bronzes of any composition between y = 3 and 2+x exhibit metallic conduction, and the tetragonal bronzes are semiconductors. The thermal coefficients of the electrical resistivity for the cubic bronzes are very small; they are minimal at x = 1.0 for the oxygen-stoichiometric bronzes (y = 3) and at x = 0.6 for the bronze having “full oxygen vacancies” (y = 2+x). Thermoelectric-power measurements have shown that the charge carriers of each bronze are electrons. The effective electron mass for the cubic bronzes does not depend on x, but on y. The mass for the oxygen-stoichiometric bronzes (y = 3) is a constant (2m_o), but the mass for the bronzes having full oxygen vacancies increases from 2m_o to 5m_o with decreasing y.     

Dielectric and ferroelectric properties of (1-x)(Na0.5K0.5)NbO3-xBaTiO3 ceramics

(1-x)(Na_0.5K_0.5)NbO₃-xBaTiO₃ ceramics were prepared by a solid state reaction approach, and their dielectric and ferroelectric properties were evaluated together with the crystal structure. Three phase transitions at T_t1, T_t2 and T_t3 were observed by the combination of DTA analysis and dielectric characterization. These phase transitions corresponded to those of (Na_0.5K_0.5)NbO₃, and they were greatly pulled down by forming solid solution with BaTiO₃. The phase transition around T_t1 was incompletely diffusive and the appearance of diffusiveness of non ferro-paraelectric phase transition was an exception. The hysteresis loops changed their shapes from “square” into “thin square” with increasing x.     

Isopropanol-assisted hydrothermal synthesis of (K, Na)NbO3 piezoelectric ceramic powders

(K, Na)NbO₃ particles were synthesized using the isopropanol-assisted hydrothermal method. The addition of isopropanol made it possible to prepare (K, Na)NbO₃ solid solutions under a mild hydrothermal condition of 2 mol/L alkali solution. The effects of the K/(K + Na) molar ratio, (K + Na)/Nb molar ratio in the starting suspensions, and annealing process on the phase evolutions of the (K, Na)NbO₃ solid solutions were investigated. The phases of the as-prepared particles were investigated by X-ray diffraction technique. The microstructure and composition were analyzed by scanning electron microscope and energy dispersive X-ray analysis. (K, Na)NbO₃ solid solutions were successfully synthesized by hydrothermal method with the addition of isopropanol through adjusting the K/(K + Na) molar ratio and (K + Na)/Nb molar ratio in the starting suspensions. The change of morphology is also in agreement with the phase evolution. The phase evolutions were discussed and the formation mechanism of the (K, Na)NbO₃ solid solutions was proposed.