Effect of cation doping on ionic and electronic properties for lanthanum silicate-based solid electrolytes

Electronic as well as ionic conducting properties for oxyapatite-type solid electrolytes based on lanthanum silicate, La_9.333 + xSi₆O_26 + 1.5x (LSO) were investigated in the oxygen-excess region (x > ca. 0.3). We have found that the oxygen excess-type LSO (OE-LSO), namely La₁₀Si₆O₂₇ on weighted basis, exhibited high conductivity, and substitution of the Si-site of LSO with some dopants (Mⁿ⁺) had a positive effect toward the conducting property. Furthermore, it was also found that addition of a very small amount of iron ions into the M-doped OE-LSO, La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y, improved its conductivity. On the other hand, replacement of the La-site with various ions for La₁₀(Si_6-yMⁿ⁺_y)O_27-(2-0.5n)y did little to improve conductivity. The electronic transport numbers for Al-doped OE-LSO with Fe-addition, (1-α){La₁₀(Si_5.8Al_0.2)O_26.9}-α(FeO_γ), evaluated with the Hebb-Wagner polarization method were very low: i.e., 1.1 × 10^− 3 and 2.9 × 10^− 3 under P(O₂) = 1.1 × 10⁴ Pa at 1073 K for α = 0.00 and 0.005, respectively. Conductivity for each sample was unchanged under humidified atmosphere at 1073 K sustained for over 50 h, revealing that both compositions were chemically stable. It was concluded that 0.995{La₁₀(Si_5.8Al_0.2)O_26.9}-0.005(FeO_γ) is suitable for the fuel cell electrolytes because of its high and almost pure ionic conductivity, and its good chemical stability under humidified as well as reducing conditions.     

Influence of boron on the giant magnetocaloric effect of La(Fe0.9Si0.1)13

The influences of boron addition on the phase formation, Curie temperature and magnetic entropy change of the NaZn₁₃-type La(Fe_0.9Si_0.1)₁₃ compound have been investigated. Eight boron containing La(Fe_0.9Si_0.1)₁₃B_x samples were prepared with x=0, 0.03, 0.06, 0.1, 0.2, 0.3, 0.5 and 0.6, respectively. Experimental results show that a small amount of B addition in La(Fe_0.9Si_0.1)₁₃ forms the solid solution NaZn₁₃-type structure phase by substituting B for Si or doping B into interstitial position of the lattice, preserves its giant magnetocaloric effects due to their first-order structural/magnetic transition, as well as increase its Curie temperature T_c slightly. The maximum magnetic entropy changes in the magnetic field change of 0–1.6 T are around 20 J kg^–1 K^–1 for the samples with Boron addition less than 0.3, while improving the Curie temperatures by 2 K.     

Effect of Co or Mn addition on the soft magnetic properties of amorphous Fe89−xZr11Bx (x=5, 10) alloy ribbons

The temperature and field dependent magnetic properties of melt-spun amorphous Fe_89−x−yZr₁₁B_x(Co,Mn)_y (x=5, 10 and 0≤y≤10) alloys in the temperature range 5-1200 K are reported. The Curie temperature and saturation magnetization at room temperature increase (decrease) almost linearly with Co (Mn) addition. With increasing Co concentration, the room temperature coercivity increases at the rate of 2.26 (0.28) A/m per at% for the x=5 (10) samples. The high-field magnetic susceptibility and local magnetic anisotropy decrease (increases) rapidly with increasing Co (Mn) concentration. The thermomagnetic curves show a marked increase in magnetization above 850 K corresponding to the crystallization of α-FeCo (α-Fe) phase in samples containing Co (Mn). The Curie temperature of the crystalline phase increases (remains same) with increasing Co (Mn) concentration with the formation of α-FeCo (α-Fe). Addition of Co up to 10 at% in Fe-Zr-B improves the room temperature saturation magnetization from 0.56 to 1.2 T, and Curie temperature from 315 to 476 K. Also, the coercivity increases with Co addition from 1.27 to 23.88 A/m for x=5 and from 7.64 to 10.35 A/m for x=10 alloy. The non-collinear spin structures that characterize Fe rich Fe-Zr-B amorphous alloys have been used to describe the observed results.     

Synthesis,structure, and properties of BIFENBVOX

Solid solutions Bi₄V_2-x Fe _x/2Nb _x/2O_11-δ (х?=?0.05–1.0) and Bi₄V_2-х-y Fe _x Nb _y O_11–δ (with fixed x or y?=?0.2 and variable х or y?=?0.2–0.5 with step 0.1) were synthesized by the standard ceramic technology in the temperature range 773–1113 K and by mechanochemical activation method using Bi₂O₃, V₂O₅ Fe₂O₃, and Nb₂O₅ oxides as initial compounds. The formation of solid solutions was studied. Ranges of stability and temperature values of phase transitions for different polymorphous modifications were defined using dylatometric and thermo gravimetric studies. The morphology and the local chemical composition of the ceramic samples were studied. Samples with concentration of dopants x?>?0.3 contain two phases; both major and impurity phases are solid solutions of the BIFENBVOX type although the dopants atoms distribution between them is random. The thermal expansion coefficients (TEC) were measured. The electrical conductivity of ceramic samples was investigated in a wide range of temperatures. The highest conductivity values among the studied solid solutions are observed for the sample with a small amount of dopants x?=?0.25.     

Specific features in the synthesis, crystal structure and electrical conductivity of BICUTIVOX

The formation of solid solutions Bi₄V_2 − xCu_x/2Ti_x/2O_11 − x (0.025 ≤ x ≤ 0.5) known as BICUTIVOX, synthesized by three different methods (a conventional solid-state synthesis, solid-state synthesis enhanced by mechanical activation, and through liquid precursors), has been studied. Based on crystal structure investigations carried out at different temperatures, ranges of stability and temperatures of phase transitions for different polymorphous modifications have been defined. The morphology and the local chemical composition of the ceramic samples obtained have been studied. Thermal expansion coefficients have been measured. The electrical conductivity of ceramic samples has been investigated in a wide range of temperatures and partial oxygen pressures.     

Substrate and orientation influence on electrical properties of sputtered La-doped PZT thin films

Pb_1−2y/3La_yZr_xTi_1−xO₃ (PLZT) thin films have been prepared “in situ” by multi-target sputtering on Silicon, LaAlO₃ (LAO) and MgO substrates covered with a Pt bottom electrode. The purpose was to grow tetragonal PLZT films (Zr/Ti = 28/72 with different La contents) on these various substrates and to compare their electrical properties. To this aim, Pt was first deposited on the three different substrates to get (1 1 1)Pt/Si, (1 1 1)Pt/LAO and (2 0 0)Pt/MgO. Then PLZT was deposited in a same run on these three kinds of substrates and the influence of La contents and film orientation on electrical properties was investigated. The La content was varied from y = 0 to y = 32 in order to explore the phase transition between ferroelectric and paraelectric phases as a function of the substrate. For large amount of Lanthanum, relaxor behavior has been observed and studied.     

Thermal, electrical, and electrochemical properties of Lanthanum-doped Ba0.5Sr0.5 Co0.8Fe0.2O3-δ

Crystal structure, thermogravimetry (TG), thermal expansion coefficient (TEC), electrical conductivity and AC impedance of (Ba_0.5Sr_0.5)_1-xLa_xCo_0.8Fe_0.2O_3-δ (BSLCF; 0.05?x?0.20) were studied in relation to their potential use as intermediate temperature solid oxide fuel cell (IT-SOFC) cathode. A single cubic pervoskite was observed by X-ray diffraction (XRD). The TEC of BSLCF was increasing slightly with the increasing content of La, and all the compounds showed abnormal expansion at high temperature. Proved by the TG result, it was associated with the loss of lattice oxygen. The electrical conductivity, which is the main defect of Ba_0.5Sr_0.5 Co_0.8Fe_0.2O_3-δ (BSCF), was improved by La doping, e.g., the compound of x=0.20 demonstrated a conductivity of σ=376 S cm⁻¹ at 392 °C. The increase of electrical conductivity resulted from the increased concentration of charge carrier induced by La doping. In addition, the AC impedance revealed the better electrochemical performance of BSLCF. For example, at 500 °C, the sample with composition x=0.15 yielded the resistance values of 2.12 Ω cm², which was only 46% of BSCF.     

在BaF2-BiF3系统中的相组成和离子电导

用固相反应法、X射线粉末衍射技术和复平面阻抗谱测量研究了BaF₂-BiF₃系统的相组成和离子电导。在此系统中发现了两种类型的Ba_1-xBi_xF_2+x固溶体:萤石型(0s≈0.5(14^1/2)a_F,c_{s< 关键词：}     

Magnetocaloric properties of LaFe13−x−yCoxSiy and commercial grade Gd

The magnetocaloric properties of three samples of LaFe_13−x−yCo_xSi_y have been measured and compared to measurements of commercial grade Gd. The samples have (x=0.86, y=1.08), (x=0.94, y=1.01) and (x=0.97, y=1.07) yielding Curie temperatures in the range 276-288 K. The magnetization, specific heat capacity and adiabatic temperature change have been measured over a broad temperature interval. Importantly, all measurements were corrected for demagnetization, allowing the data to be directly compared. In an internal field of 1 T the maximum specific entropy changes were 6.2, 5.1 and 5.0 J/kg K, the specific heat capacities were 910, 840 and 835 J/kg K and the adiabatic temperature changes were 2.3, 2.1 and 2.1 K for the three LaFeCoSi samples respectively. For Gd in an internal field of 1 T the maximum specific entropy change was 3.1 J/kg K, the specific heat capacity was 340 J/kg K and the adiabatic temperature change was 3.3 K. The adiabatic temperature change was also calculated from the measured values of the specific heat capacity and specific magnetization and compared to the directly measured values. In general an excellent agreement was seen.     

Theoretical investigation of the conduction and valence band offsets of GaAs1−x Nx/GaAs1−yNy heterointerfaces

Theoretical investigations of the conduction band offset (CBO) and valence band offset (VBO) of the relaxed and pseudo-morphically strained GaAs_1−xN_x/GaAs_1−yN_y heterointerfaces at various nitrogen concentrations (x and y) within the range 0-0.05 and along the [0 0 1] direction are performed by means of the model-solid theory combined with the empirical pseudopotential method under the virtual crystal approximation that takes into account the effects of the compositional disorder. It has been found that for y < x, the CBO and VBO have negative and positive signs, respectively, whereas the reverse is seen when y > x. The band gap of the GaAs_1−xN_x over layer falls completely inside the band gap of the substrate GaAs_1−yN_y and thus the alignment is of type I (straddling) for y < x. When y > x, the alignment remains of type I but in this case it is the band gap of the substrate GaAs_1−yN_y which is fully inside the band gap of the GaAs_1−xN_x over layer. Besides the CBO, the VBO and the relaxed/strained band gap of two particular cases: GaAs_1−xN_x/GaAs and GaAs_1−xN_x/GaAs_0.98N_0.02 heterointerfaces have been determined.     

Development of a high-throughput thermoelectric screening tool for combinatorial thin film libraries

We have developed a high-throughput thermoelectric screening tool for the study of combinatorial thin films. This tool consists of a probe to measure resistance and Seebeck coefficient on an automated translation stage. A thin film library of the (Ca_1−x−ySr_xLa_y)₃Co₄O₉ ternary system has been fabricated on a Si (1 0 0) substrate, using combinatorial pulsed laser deposition by the natural-composition-spread method. We have demonstrated successful mapping of the resistance and Seebeck coefficient of this film library. The mapping indicates that the substitution of La for Ca results in an increase of both resistance and Seebeck coefficient, and that of Sr results in a decrease of resistance. The screening tool allows us to measure 1080 data points in 6 h.     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Highly cation-deficient manganese perovskite, La1−xMn1−yO3 with x=y

Oxidative (δ>0) nonstoichiometry in the perovskite ‘LaMnO_3+δ’ has been known to be manifested not with O interstitials but rather with cation vacancies of equal amounts at the two cation sites, La and Mn, i.e. La_1−xMn_1−yO₃ with x=y. Here, we report the fabrication of samples with record-high cation-vacancy concentrations (x>0.12 or δ>0.4) by means of a variety of high-pressure oxygenation techniques. Linear (negative) dependence of the cell volume on x was observed within the whole x range investigated, down to 56.9 Å³ (per formula unit) for a sample oxygenated at 5 GPa and 1100 °C using Ag₂O₂ as an excess oxygen source. With increasing degree of cation deficiency in La_1−xMn_1−xO₃, the ferromagnetic transition temperature was found to follow a bell shape with respect to x exhibiting a maximum of ∼250 K about x≈0.1. For moderately oxygenated samples large magnetoresistance effect was evidenced.     

Photoluminescence scanning on InAs/InGaAs quantum dot structures

The photoluminescence spectra of InAs quantum dots (QDs) embedded into four types of In_xGa_1−xAs/GaAs (x = 0.10, 0.15, 0.20 and 0.25) multi quantum well MBE structures have been investigated at 300 K in dependence on the QD position on the wafer. PL mapping was performed with 325 nm HeCd laser (35 mW) focused down to 200 μm (110 W/cm²) as the excitation source. The structures with x = 0.15 In/Ga composition in the In_xGa_1−xAs capping layer exhibited the maximum photoluminescence intensity. Strong inhomogeneity of the PL intensity is observed by mapping samples with the In/Ga composition of x ≥ 0.20-0.25. The reduction of the PL intensity is accompanied by a gradual “blue” shift of the luminescence maximum at 300 K as follows from the quantum dot PL mapping. The mechanism of this effect has been analyzed. PL peak shifts versus capping layer composition are discussed as well.     

First-principles calculations to investigate optical properties of ByAlxIn1−x−yN alloys for optoelectronic devices

First-principles density-functional theory of Full-Potential Linear Augmented Plane Wave (FP-LAPW) within local density approximation (LDA) of the optical properties of B_yAl_xIn_1−x−yN systems (with x = 0.187 and y = 0.062, 0.125 and 0.187) has been performed. Substitutional atoms of Boron induced in small amounts into the (Al_xIn_1−x)-cationic sublattice of AlInN affects the energy gap of BAlInN. The higher band gap of Al_0.375In_0.625N alloy can form a useful quantum well (QW) laser structure. A best choice of B-content, B_yAl_xIn_1−x−yN could be an alternative to Al_xIn_1−xN. The results of accurate calculations of the band structures and optical properties show the better performance characteristics belong to the structure containing B-content (y) of 12.5%. The NaCl metallic B_yAl_0.1875In_0.8125−yN has a direct character for y = 12.5%. The imaginary part of dielectric function, reflectivity, refractive index, absorption coefficient and optical conductivity are investigated well and provide reasonable results for optoelectronic devices applications.     

Structural and magnetic properties of Li-Cu mixed spinel ferrites

Li_0.5−x/2Cu_xFe_2.5−x/2O₄ (where x=0.0-1.0) ferrites have been prepared by solid-state reaction. X-ray diffraction was used to study the structure of the above investigated ferrites at various sintering temperatures. Samples were sintered at 1000, 1100 and 1200 °C for 3 h in the atmosphere. For the sintering temperature of 1000 °C, Li_0.5−x/2Cu_xFe_2.5−x/2O₄ undergoes cubic to tetragonal transformation for higher Cu content. However, for the sintering temperature of 1100 and 1200 °C, X-ray diffraction patterns are mainly characterized by fcc structure, though presence of tetragonal distortion was found by other temperature dependence of initial permeability curves. The lattice parameter, X-ray density and bulk density were calculated for different compositions. Curie temperature was measured from the temperature dependence of initial permeability curves. Curie temperatures of Li-Cu mixed ferrites were found to decrease with the increase in Cu²⁺ content due to the reduction of A-B interaction. As mentioned earlier, temperature dependence of initial permeability curves was characterized by tetragonal deformation for the samples containing higher at% of Cu. The complex initial permeability has been studied for different samples. The B-H loops were measured at constant frequency, f=1200 Hz, at room temperature (298 K). Coercivity and hysteresis loss were estimated for different Cu contents.     

Phase transition, structural and electrical properties of Pb(Zn1/3Nb2/3)O3-doped Pb(Ni1/3Nb2/3)O3-PbTiO3 ceramics prepared by solid-state reaction method

Phase pure perovskite (1−x−y)Pb(Ni_1/3Nb_2/3)O₃-xPb(Zn_1/3Nb_2/3)O₃-yPbTiO₃ (PNN-PZN-PT) ferroelectric ceramics were prepared by conventional solid-state reaction method via a B-site oxide mixing route. The PNN-PZN-PT ceramics sintered at the optimized condition of 1185 °C for 2 h exhibit high relative density and rather homogenous microstructure. With the increase of PbTiO₃ (PT) content, crystal structure and electrical properties of the synthesized PNN-PZN-PT ceramics exhibit successive phase transformation. A morphotropic phase boundary (MPB) is supposed to form in (0.9−x)PNN-0.1PZN-xPT at a region of x=32-36 mol% confirmed by X-ray diffraction (XRD) measurement and dielectric measurement. The MPB composition can be pictured as providing a “bridge” connecting rhombohedral ferroelectric (FE) phase and tetragonal one since crystal structure of the MPB composition is similar to both the rhombohedral and tetragonal lattices. Dielectric response of the sintered PNN-PZN-PT ceramics also exhibits successive phase-transition character. 0.64PNN-0.1PZN-0.26PT exhibits broad, diffused and frequency dependent dielectric peaks indicating a character of diffused FE-paraelectric (PE) phase transition of relaxor ferroelectrics and 0.40PNN-0.1PZN-0.50PT exhibits narrow, sharp and frequency independent dielectric peaks indicating a character of first-order FE-PE phase transition of normal ferroelectrics. The FE-PE phase transition of 0.56PNN-0.1PZN-0.34PT is nearly first-order with some diffused character, which also exhibits the largest value of piezoelectric constant d₃₃ of 462pC/N.     

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.     

Electrical conductivity and complex electric modulus of titanium doped nickel-zinc ferrites

The samples Ni_1+x−yZn_yTi_x Fe_2−2xO₄; y=0.1, 0.0≤x≤0.5 were prepared in a single-phase spinel structure as indicated from X-ray analysis. Electrical conductivity and dielectric measurements at different temperatures from 300 K to 600 K in the frequency range from 42 Hz to 5 MHz have been analyzed. The relation of conductivity with temperature revealed a semiconductor to semimetallic behavior as Ti⁴⁺ concentration increases. The conduction mechanism depends mainly on the valence exchange between the different metal ions in the same site or in different sites. The dielectric constant as a function of temperature and frequency showed that there is a strong dependence on the compositional parameter x. The electrical modulus has been employed to study the relaxation dynamics of charge carriers. The result indicates the presence of correlation between motions of mobile ion charges. The activation energies extracted from M′(ω) and M″(ω) peaks are found to follow the Arrhenius law. The electrical conductance of the samples found to be dependent on the temperature and frequency.     

Structure dependence of near-infrared stimulated blue emission in polycrystalline Ln2(WO4)3 (Ln=Gd and Lu) doped with Tm and Yb

Tm- and Yb-doped gadolinium tungstate, (Gd_xTm_yYb_1−x−y)₂(WO₄)₃ (x=0.7-0.9; y=0.001-0.01), have been prepared by the polymerized complex method to achieve a homogeneous dispersion of dopants and to stabilize the host structure. Decomposition (900 °C 5 h) of the precursors with x=0.8-0.9 yielded a pure monoclinic phase, while that of x=0.7 resulted in formation of an orthorhombic impurity. The monoclinic phase exhibits bright up-converted blue emission due to the ¹G₄→³H₆ transition of Tm³⁺ (472 nm) upon excitation into the Yb³⁺:²F_7/2→²F_5/2 absorption band as a result of energy transfer from Yb to Tm. The orthorhombic impurity acts as a strong quencher of emission, and the quenching mechanism has been discussed on the basis of structural and spectroscopic properties of orthorhombic Lu₂(WO₄)₃:Tm,Yb prepared by the same method.